GB2032442A

GB2032442A – Petroleum resins
– Google Patents

GB2032442A – Petroleum resins
– Google Patents
Petroleum resins

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Publication number
GB2032442A

GB2032442A
GB7841463A
GB7841463A
GB2032442A
GB 2032442 A
GB2032442 A
GB 2032442A
GB 7841463 A
GB7841463 A
GB 7841463A
GB 7841463 A
GB7841463 A
GB 7841463A
GB 2032442 A
GB2032442 A
GB 2032442A
Authority
GB
United Kingdom
Prior art keywords
feed
resin
olefins
limonene
diolefins
Prior art date
1978-10-20
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Withdrawn

Application number
GB7841463A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

ExxonMobil Technology and Engineering Co

Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1978-10-20
Filing date
1978-10-20
Publication date
1980-05-08

1978-10-20
Application filed by Exxon Research and Engineering Co
filed
Critical
Exxon Research and Engineering Co

1978-10-20
Priority to GB7841463A
priority
Critical
patent/GB2032442A/en

1979-10-19
Priority to EP19790302270
priority
patent/EP0011393B1/en

1979-10-19
Priority to DK443179A
priority
patent/DK156959C/en

1979-10-19
Priority to JP13504579A
priority
patent/JPS5556113A/en

1979-10-19
Priority to CA000338041A
priority
patent/CA1185399A/en

1979-10-19
Priority to DE7979302270T
priority
patent/DE2964374D1/en

1980-05-08
Publication of GB2032442A
publication
Critical
patent/GB2032442A/en

1987-09-30
Priority to JP24775187A
priority
patent/JPS6399207A/en

Status
Withdrawn
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins

Description

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GB 2 032 442 A
SPECIFICATION Improved Petroleum Resins
The present invention relates to new improved petroleum resins and a process for their production. In particular the invention relates to resins suitable as tackifiers for elastomers and useful in hot melt formulations.
Petroleum resins obtained by the polymerisation of C5 dienes such as pentadiene 1,3 and/or isoprene are well known as is their use as tackifiers for elastomers and as components in hot melt formulations.
It is known that SIS block copolymers (block styrene-isoprene copolymers such as Shell Cariflex TR 1107) can be tackified by petroleum resins of narrow molecular weight distribution produced by controlling the polymerisation conditions with branched reactive olefins, substituted aromatics or tertiary alkyl halides, see for example our prior patent applications 31878/75 (Serial No. 1,537,852) and 33705/75 (Serial No. 1,538,057). These previously described petroleum resins of narrow molecular weight distribution tackify oil extended random SBR (styrene-butadiene) copolymers and provide very good tackifying properties for the SIS block copolymers. However, they also have a low cohesive strength in pressure sensitive adhesives based on natural rubber. They do not however tackify oil free SBR elastomers of either random or block thermoplastic nature (e.g. SBS block copolymers).
Other petroleum feed additives for example dicyclopentadiene, methyl cyclopentadiene dimers or thermal polymers obtained from cyclodiene dimer, rich streams as described in our Patent Specification U.K. 1,486,211 are known as a means of making resins of high softening point. However the resins produced in this way have degradated resin Gardner colour and wax compatibility. Moreover even if they increase the cohesive strength of pressure sensitive adhesives based on natural rubbers and slightly tackify SIS block copolymers they do not tackify other SBR copolymers.
One disadvantage of these earlier techniques is that the presence of the molecular weight controlling additive tends to reduce the softening point of the resin thus rendering it unsuitable for certain pressure sensitive adhesives particularly those where cohesive strength (shear adhesion) is important. It has been proposed to overcome this problem by carrying out the polymerisation in a paraffinic solvent which is not entirely satisfactory and increases costs and reduces plant capacity.
In our copending application No. 27941/78 (Serial No. 2,027,721) we suggest that these disadvantages may be overcome by the copolymerisation of carene with the petroleum resin feed. We have now found that similar benefits may be obtained if limonene is used instead of carene.
U.S. 3,466,267 patent describes the manufacture of resins by spiking a concentrate of a mixture of limonene and carrestrene with 10 to 50 percent by weight of piperylene. According to this patent if less than 10 percent by weight of piperylene is used the resin has an undesirably low softening point whilst if more than 50 wt.% by weight of the resin is employed softening points are lowered and the resin yields from the polymerisation are uneconomically low, the ratio of limonene to sylvestrene varies from 1:0.66 to about 1:10.
We have now found that: a satisfactorily high resin softening point (70 to 160°C and preferably 100 to 130°C) resin is achieved when more than 50 wt.% by weight of iperylene is combined with limonene without any need for carvestrene addition and that the resin yield is acceptable and has good colour stability. We have also found that the resin quality may be further improved when the limonene piperylene or other C5 conjugated diolefins such as isoprene are combined with branched olefins as transfer agents for resin molecular weight control.
The present invention therefore provides a process which comprises copolymerising using a Friedel Crafts catalyst (1) a petroleum resin feed comprising C5 olefins and diolefins, C6 olefins and diolefins or a mixture of C5 and Ca olefins and diolefins, said feed being obtained from the cracking of petroleum feedstock and (2) limonene in the absence of sylvestrene.
The present invention further provides a process which comprises copolymerising using a Friedel Crafts catalyst (1)a petroleum resin feed comprising C5 olefins and diolefins, C6 olefins and diolefins or a mixture of C5 and C6 olefins and diolefins, said feed being obtained from the cracking of petroleum feedstocks and (2) limonene the petroleum resin feed comprising at least 40 wt.% of the combined weight of the resin feed and limonene.
The present invention further provides the petroleum resin prepared according to the processes described above.
The C5 or C6 diolefin and olefin containing feed used in our process may be obtained from the cracking of petroleum feedstock: Such feedstocks include naphthas, kerosene, gas oil and vacuum gas oil. These feedstocks usually boil in a range of from 20°C to 450°C.
The petroleum feedstock is cracked, preferably in the presence of steam, and the recommended cracking temperature is between 500° and 870°C. The product which contains unsaturated hydrocarbons usually boiling in the range of 20° to 240°C, preferably 20° to 130°C, usually is thereafter subjected to fractionation to remove C2 to C4 light ends. The feedstock may thereafter be subjected to thermal soaking at a temperature of between 100°C and 160°C, preferably 120° to 140°C, e.g. about 130°C. The thermal soaking preferably takes 0.5 to 6 hours, e.g. 0.5 to 1 hour. Low temperatures are preferred in order to limit the cyclic diene (Cyclopentadiene and
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2
GB 2 032 442 A 2
Methylcyclopentadiene (co-dimerization with C5 linear conjugated dienes (isoprene and pentadienes 1,3 cis- and trans-). After fractionation and if carried out thermal soaking, the feedstock is preferably subjected to distillation to remove cyclic conjugated diolefins which are gel precursors (cyclopentadiene and methylcyclopentadiene being removed as dimers).
5 After distillation one obtains an overhead naphtha which usually boils in the range from 25 to 5
110°C, e.g. 25 to 80°C, the best results being achieved with a 25—70°C cut. This overhead naphtha comprises mainly C5 diolefins such as isoprene and 1,3 cis- and trans- pentadienes, C5 to C6 mono-olefins and aromatics for example benzene. In general the overhead naphthas have the following compositions:
10 % by weight 1 g
Total paraffins 1.0 to 41.5
Total diolefins 35.5 to 14.5
Total olefins 33.5 to 13.0
Total aromatics 30.0 to 31.0
15 Isoprene 16.5 to 6.5 15
Pentadiene 1,3 15.5 to 4.5
Cyclopentadiene 1.0 to 2.5
the exact composition depending on the nature of the petroleum feedstock which is subjected to steam cracking.
20 The feed could be significantly isoprene free provided this compound is previously recovered 20
through any conventional extraction process such as extractive distillation or azeotropic distillation. In such cases the properties of the resins produced are better than those obtained with isoprene-containing feeds. Moreover, depending on the final boiling point of the feed cut the feedstock could be substantially free of benzene. Cyclopentene contents are generally below 3 wt.%.
25 If thermal soaking has been carried out the cyclodiene dimers which are produced are generally 25
not included ii>the feed to be polymerised, because they are detrimental to the specific properties of the resins. However, if required for special applications they can be left in the resin feed, the distillation step previously mentioned being carried out before the thermal soaking step.
In our preferred process 50.1 to 99 wt.% more preferably 50.1 to 85 wt.% of piperylene and/or
30 isoprene based on the combined weight of C5 conjugated diolefins and limonene should be used. The 30 limonene used may be a concentrate obtained from gum or crude sulphate turpentine by rectification,
such a concentrate generally contains from 50 to 85 wt.% of limonene. Two samples of a typical stream were found to contain:
‘inene 0.2 wt.% 0.1 wt.%
35
40
We found that the use of limonene narrows the molecular weight distribution of the resin at the same time increasing the softening point of the resin.
45 The techniques of the present invention are equally applicable to resin production processes which 45
employ other agents to narrow the molecular weight distribution such as the branched reactive olefins of our application 33705/75 to achieve extremely narrow distribution without reduction of softening point. Similarly the limonene may be incorporated into systems which uses a solvent to keep up softening points or the need for the solvent may be obviated by the use of the limonene. The ratios of 50 the amount of limonene and petroleum resin feed to the amount of branched olefine used may be 50
varied to obtain resins of any desired softening point within the range 60°C to 140°C. Where branched olefins are used a broad (e.g. C5—C8) fraction of our U.K. application 33705/75 may be used. The preferred branched olefins are oligomers of propylene and butylenes obtained with phosphoric acid catalysts (called U.O.P. olefins) or from a Fluid Catalytic Cracker (F.C.C. olefins) or from stream 55 cracking. Typical compositions are shown in Tables 1 and 2. 55
Other chain transfer agents such as the alkyl halides of our U.K. application 31878/75 may also be used.
In addition C8—C10 polymerisable unsaturated aromatic monomers such as styrene, ar-methyl styrene, vinyl toluene, indene, methyl indene (see U.S. 4,078,132) may also be included in the 60 polymerisation mixture which we find improves the compatibility of resin especially for use in hot melt 60 applications. Chloro and polar styrene (e.g methoxy styrene) derivatives are other potentially attractive monomers.
The resin feed and the limonene are mixed and polymerised using a Friedel Crafts catalyst, for example aluminium chloride, aluminium bromide or a liquid aluminium chloride/hydrochloric acid alkyl 65 substituted aromatic hydrocarbon complex, the aromatic hydrocarbon being for example o-xylene, 65
a-Pinene
0.2 wt.%
0.1 wt.%
35
Camphene
0.1 wt.%
—
/3-Pinene
0.1 wt.%
—
A-3 Carene
6.9 wt.%
5.0 wt.%
a;-Terpinene
3.0 wt.%
3.3 wt.%
p-Cymene
5.5 wt.%
5.1 wt.%
40
Limonene
74.3 wt.%
78.8 wt.%
p-Terpinene
1.1 wt.%
1.1 wt.%
Terpinolene
1.5
3.2 wt.%
3 GB 2 032 442 A
mesitylene, ethyl benzene, isopropyl benzene and other short or long chain alkyl benzenes. The alkyl chain can be linear or branched and can vary from 1 to 30 carbon atoms.
Acid liquid AICI3 sludges obtained as by-products during the alkylation of benzene or any other substituted aromatics (e.g. toluene or xylenes) with branched chain olefins can be directly used as 5 catalyst for the above described polymerisation process. The branched chain olefins which are for example, produced via the boron trifluoride, oligomerisation of propylene and/or butylene and fractionation, e.g. C12 olefins or C24 olefins, can be alkylated with aromatics producing in situ sludge. As an example the acidic sludge available from a dodecylbenzene plant provided similar results to the preformed o-xylene AlClg/HCI liquid complex.
10 These liquid complexes are slightly more efficient that AICI3 powder at equivalent concentration and provide slightly higher resin yields and lower resin molecular weight. Therefore, the amount of limonene required for narrowing the resin molecular weight is significantly reduced. Moreover when by-product sludges are available in plant site, the catalyst cost is reduced and such a process is particularly attractive although powdered AICI3 results in resin having better Gardner colour. 15 In the polymerisation process the amount of catalyst may vary from 0.25 to 3.0 wt.% preferably 0.5 to 1.5 wt.% based on the weight of the mixture to be polymerised. The optimum concentration depends on the nature of the solvent which affects the solubility of the catalyst as well as on the stirring efficiency inside the polymerisation reactor. High catalyst concentration reduces the resin molecular weight distribution and therefore limits the amount of limonene required for controlling the 20 resin molecular weight.
Other Friedel Crafts catalysts like titanium tri- or tetrachloride, tin tetrachloride, boron trifluoride, boron trifluoride complexes with organic ethers, phenols or acids can also be used but they lead to rather low resin yields and large quantities of liquid oligomers of low value are obtained. Even though these oily oligomers can be upgraded as reactive plasticizer or liquid plasticizer such catalysts are not 25 recommended. Other possible catalysts can be acidic clays.
Usual polymerisation temperatures are between —20°C and 100°C, preferably between 30° and 80°C.
After polymerisation the residual catalyst may be removed by for example, washing with aqueous solution of alkali, ammonia or sodium carbonate, or by the addition of an alcohol such as methanol and 30 subsequent filtration.
The final resin may be stripped of unreacted hydrocarbons (“raffinate” rich in benzene and/or paraffins/unreactive olefins) and low molecular weight oil oligomers by stream stripping or vacuum distillation. The finished product is a substantially non-aromatic unsaturated thermoplastic hydrocarbon resin. It usually has a softening point of from 70°C to 160°C, preferably 100° to 130°C. 35 The resins obtained can be used in many applications which require low viscosity, good flexibility and elongation before or especially after chemical modification with molar compounds such as phenols, unsaturated anhydrides such as maleic anhydride or unsaturated acids (e.g. fumaric acid). These resins are designed for a wide range of end uses and applications. They can be applied to paper, metal, thermoplastic films (cellophane, polyesters, PVC, woven or non woven fabrics, glass etc. da for 40 bonding such materials together). Typical application are hot melts, carpet backing, coating with drying oil formulation, book binding, paper sizing or in any applications involving natural or synthetic resins and/or rubbers such as caulks, sealants or rubber tackification. More especially they may be used as tackifiers with natural rubber or synthetic rubbers such as polyisoprene. EPDM, butyl, chlorobutyl, bromobutyl, neoprene and block copolymers for example styrene/isoprene rubber (Shell Cariflex TR 45 1107) mixtures of such rubbers. Even though these resins are significantly non-aromatic they provide outstanding tackiness with such elastomers and high resin/rubber ratio can be used to reducing the adhesive formulation cost (the resin being significantly cheaper than the block thermoplastic styrene/isoprene/styrene rubber).
Other applications involving such resin properties are pressure sensitive adhesives, hot melt 50 adhesives, low temperature adhesives, label adhesives, latex adhesives, surgical tapes and masking tapes where they may be blended with polymers such as ethylene/vinyl acetate copolymers optionally blended with wax.
Thus, hot melt adhesives and latex adhesives can be prepared from styrene-isoprene block copolymers and a tackifying resin. The low softening point aliphatic petroleum resins are a replacement 55 for aromatic resins or resin and terpene derivatives.
The present invention is illustrated but in n.o way limited by reference to the following examples. Example 1
The limonene rich stream described above, a piperylene rich stream comprising:
Pentadiene 1:3 Trans 48.5 wt.%
60 Pentadiene 1:3 Cis 23.6 wt.%
Cyclopentene 17.5 wt.%
Cyclopentane 8.1 wt.%
Others (Paraffins/olefins etc) 2.3 wt.%
_3_
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and/or a fluid catalytic cracker olefine stream of Final Boiling Point 100°C containing:
4
GB 2 032 442 A 4
33.90 wt.% Paraffins 0.33 wt.% diolefins 58.40 wt.% olefins 0.11 wt.% aromatics
5 Total C4 17.15 wt.% 5
were fed to a 2 litre giass reactor in the ratios given in Table 1 below. The reactor was fitted with a mechanical stirrer, a cooler and catalyst injection device. 1 wt.% of powdered AICI3 as catalyst based on the total weight of the feed was injected into the reactor which was then held at 50°C for 90 minutes.
10 The solvent used contained: 10
99.44 wt.% paraffins 0.50 wt.% aromatics 0.06 wt.% unknown and contained 10 parts per million of sulphur.
15 The properties of the resins obtained are also given in Table 3. 15
Example 2
The effect of the presence of both limonene and fluid catalytic cracked olefins on the softening point and the molecular weight distribution with and without the paraffinic solvent was assessed using the reactor used in Example 1. The pentadiene 1:3 feed consisted of:
20 Pentadiene 1:3 Trans 42.7 wt.% 20
Pentadiene 1:3 Cis 24.2 wt.%
Cyclopentene 17.5 wt.%
_ Cyclopentane 8.5 wt.%
Other 7.1 wt.%
25 and the polymerisation conditions were as in Example 1. The results are shown in the following Table 25 4, together with the properties of the products obtained {same test methods as in Example 1).
Example 3
For comparison purpose the effect of Limonene and A-3 Carene are shown respectively in Table 5 and 6. The pentadiene 1,3 feed composition and the polymerisation conditions were those of Examples 30 1 and 2. 30
Table 6 shows that the resins produced according to the present invention exhibit excellent ■tackifying properties for both natural and thermoplastic block copolymers such as Shell Cariflex (Registered Trade Mark) TR 1107.
The composition of A-3 Carene is shown in Table 7.
35 Example 4 35
In this example the piperylene rich stream is replaced by a conventional C5 petroleum resin feed containing both isoprene and piperylene (composition described In Table 8) and the relative eTfect of spiking such a feed with Limonene is compared with those of commercially available streams like dipentene, a and /3-Pinene, (composition shown in Table 9).
40 Resins properties are described in Table 10. 40
Since /3-pinene is the main component in the manufacturing process of polyterpene resins its use is shown for comparative purpose. Its impact on resin softening point is very pronounced but it leads to higher molecular weight than limonene and Carene.
Table 1
45 Composition of C5—C8 U.O.P. Olefin Additives 45
Gas Chromatography Analysis (After Hydrogenation)
Peer’s:
C6’s:
50 C7’s: 24.78 29./I ZV.GV 50
C8 s:
C9’s:
C9’s and higher REID Vapor Pressure (ASTM d 323)
55 at20°C 0.39 bar 0.55 bar 0.57 bar 55
at 33°C 0.75 bar 1.08 1.07
Bromine number Br/100 g 125 84 74
Sulfur (ppm) 6 10 5
Mercaptans (ppm) 1
3.39
12.67
11.03
4.73
6.94
12,34
25.70
37.61
32.55
24.78
29.71
20.60
35.50
12.48
23.02
0.78
0.78
0.41
4.34
0.46
5
5
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15
20
•25
30
35
40
45
50
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60
5
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GB 2 032 442 A
Table 1 (cont.)
Ultra-violet Fluorescence Indicator Analysis
Olefins vol.%
80
56
40
Paraffins vol.%
20
44
60
Paraffins Content {wt.%)
After olefin absorption with
mercuric perchlorate
43.7
52.3
Table 2
Gas Chromatographic Analysis of Fluid Catalytic
Cracked Olefin Fraction
Overall Composition (wt.%)
Total Paraffins
33.90
35.07
35.33
Total Diolefins
0.33
0.32
0.90
Total Olefins
58.40
56.43
59.13
Total Aromatics
0.11
0.50
2.31
Unidentified
7.26
7.68
2.33
Specified gravity at 15°C
0.6457
0.6614
0.6801
Olefin Fraction
Boiling Range °C
25—50
25—70 25—100
C4’s
16.09
11.04
7.09
Cs s
38.25
28.33
19.78
C6’s
5.37
20.18
32.01
Table 3
Feed Composition
Limonene Concentrate (wt.%)
40
33
26
33
Solvent (wt.%)
30
35
35
17
Benzene (wt.%)
30
—
—
—
Pentadiene 1:3 concentrate (wt.%)
32
39
32
Fluid cat cracker olefine (wt.%)
—
—
18
Limonene in Total Feed (wt.%)
29.7
24.1
19.3
24.5
Pentadiene in Total Feed (wt.%)
23.0
28.1
23.0
Pentadiene on combined Pentadiene+Limonene
(based on exact concentration in feed)
48.8
59.3
48.4
Product
Resin (wt.%)
6.2
43.6
42.6
47.8
Liquid Oligomers (wt.%)
13.2
8.6
5.6
11.6
Unreacted Compounds (wt.%)
80.6
47.8
51.8
40.6
Product Properties
Resin softening point ASTM E-28 (°C)
115
144
146
124
Gardner Colour ASTM D-1544
11
2+
3-
3
Heat stability
(colour after 16 hrs at 150°C)
13.5
10
7
12+
Wax cloud point °C Wax/resin/EVA*
50:25:25 Molecular wt. G.P.C.
Mn^
Mw
Mw/Mn
Pressure Sensitive Adhesive Properties (Resin: Natural Rubber=50:50 wt.) 180° Peel Strength (PSTC-1**)
70
250+
1735 10920 6.23
250+ 1370
83
4330 3.16
1 lbs/inch)
3.0
2.6
2.1
2.8
Polyken Tack (grams) ASTM D-2979
1100
300
300
1050
Tack Rolling Ball (cm) PSTC-6
2
30+
30+
4.5
178° Holding Power PSTC-7
(hours to failure)
27
500
500
131
•Ethylene/vinyl Acetate copolymer containing 28 wt.9 •Wax having a melting point of 65°C.
••Pressure sensitive Tape Council Test Method.
vinyl acetate and of Melt Index 12—18.
6
Gfi 2 032 442 A 6
Table 4
Feed Composition
Limonene concentrate (wt.%)
—
—
20
20
33
Solvent (wt.%)
30
—
—
—
17
F.C.C. olefins (wt.%)
41
58
40
48
18
Pentadiene 1,3 concentrate (wt.%)
29
42
40
32
32
Limonene in Total Feed (wt.%)
—
—
14.9
14.9
24.3
Pentadiene in Total Feed (wt.%)
19.4
28.0
28.8
23.0
23.0
Product
Resin (wt.%)
27.8
40.0
49.4
42.0
47.4
Liquid Oligomers (wt.%)
5.2
6.3
11.2
15.4
11.6
Unreacted Compounds (wt.%)
67.0
53.7
39.4
36.6
40.0
Product Properties
Softening Point
100
93
112
113
124
Gardner Colour
4-
3+
3.5
3.5
3
Heat Stability
14
13.5
13.5
12-
12+
Molecule Wt Mn
1350
1295
1420
1370
Mw
2990
2350
4205
4330
Mw/Mn
2.21
1.81
2.96
3.16
Wax Cloud Point °C
50:25:25
72
70
76
69
83
180° Peel Strength (lb/inch)
2.1
2.2
2.3
2.3
2.8
Polyken Tack (grams)
950
870
950
1000
1050
Tack Rolling Ball (cm)
2
1
2.5
2.5
4.5
178° Holding Power
62
27
123
53
131
–
Table 5
Comparison of Carene and Limonene
Feed Composition
Carene Concentrate (wt.%)
20
25
—
30
Solvent (wt.%)
40
37.5
37.5
Limonene (wt.%)
—
—
25
Pentadiene 1:3 concentrate (wt.%)
20
25
25
Fluid cat cracker olefine (wt.%)
20
12.5
12.5
Carene in Total Feed (wt.%)
16.8
20.9
1.2
35
Limonene in Total Feed (wt.%)
—
—
19.7
Pentadiene in Total Feed (wt.%)
14.4
18.0
18.0
Product
Resin (wt.%)
27.2
33.4
35.2
Liquid oligomers (wt.%)
10.4
11.8
10.8
40
Unreacted Compounds (wt.%) Product Properties
62.4
54.8
54.0
Resin softening point ASTM E-28°C
112
112
108
Gardner colour ASTM D-1544
3.5
3.5
4.5
Heat stability
45
(colour after 16 hrs at 150°C) Wax cloud point °C Wax/resin/EVA**
12.5
11
12.5
50:25:25
68
68
68
40:40:20
86
84
80
50
Molecular wt. G.P.C.
Mn^
Mw
Mw/Mn
Pressure Sensitive Adhesive Properties
1190 2265 1.907
55
(resin: Natural Rubber=50:50 wt) 180° Peel Strength (PSTC-1**
1 lbs/inch)
2.95
3.10
2.85
Polyken Tack (grams) ASTM D-2979
1150
1300
1100
Tack Rolling Ball (cm) PSTC-6
1.5
1.5
2
60
178° Holding Power PSTC-7
(hours to failure)
23
18
42
5
10
15
20
25
30
35
40
45
50
55
60
•Ethylene/vinyl Acetate copolymer containing 28 wt.% vinyl acetate and of Melt Index 12—18. *Wax having a melting point of —65°C.
••Pressure sensitive Tape Council Test Method.
7
5
10
15
20
25
30
35
40
45
50
GB 2 032 442 A 7
Table 6
Comparison of Limonene and A-3 Carene
Feed Composition
Limonene concentrate (wt.%)
12.5
—
Carene concentrate (wt.%)
—
12.5
5
F.C.C. olefines (wt.%)
51.0
51.0
Pentadiene 1,3 concentrate (wt.%)
36.5
36.5
Limonene in Total Feed (wt.%)
9.8
0.9
Carene in Total Feed (wt.%)
0.6
10.5
Pentadiene in Total Feed (wt.%)
24.4
24.4
10
Product
Resin (wt.%)
41.2
39.8
Liquid oligomers (wt.%)
10.4
10.0
Unreacted compounds (wt.%)
48.4
60.2
Product Properties
15
Softening point
98
100
Gardner Colour
4-
4-
Heat Stability
14
14.5
Molecular Wt. Mn
1145
1285
Mw
2150
2400
20
Mw/Mn
1.87
1.86
Wax Cloud Point °C
50:25:25
<68 <68 40:40:20 75 88 Pressure Sensitive Adhesive Properties 25 (Resin/Rubber ratio 50/50 wt.%) Rubber Type NR(1» TR 1107(2) NR'11 TR 110 180° Peel Strength lb/inch) 2.65 5.5 2.45 6.0 Polyken Tack (grams) 1100 1600 1150 1600 Tack Rolling Ball (cm) 1.5 2 1.5 2.5 30 178° Holding Power 46 500+ 64 500+ (1) Natural Rubber 65 Mooney Viscosity. (2) Shell block copolymer TR 1107 (styrene — isoprene — styrene). Table 7 A-3 Carene Concentrate (Typical) by Gas Chromatography /3-Pinene 1.8 A-3 Carene 83.9 a-Terpinene 0.5 /j-Cymene 1.7 Limonene 7.4 Terpinolene 0.6 Unidentified Difference to 100.0 35 40 Table 8 Typical Composition of a Steam Cracked Petroleum Feedstock Boiling Point °C (25—70) by Gas Chromatography Overall Composition Paraffins C5 to C6 conjugated diolefins C5 to C6 olefins Benzene 2.1 50.0 43.8 3.4 45 50 Typical Cs Diolefins Isoprene Pentadiene 1,3 trans Pentadiene 1,3 cis Cyclopentadiene 23.7 11.8 7.9 1.8 1, 9.7 55 Typical C5 Olefins 2 Methyl butene 1 2 Methyl butene 2 Pentene 1 Cyclopentene 8.5 6.4 7.4 4.8 60 8 GB 2 032 442 A 8 Table 9 Typical Composition of Commercial Dipentene and Terpenes Stream by Gas Chromatography 10 15 20 Product Source a-Pinene Camphene /3-Pinene Carene a-Terpinene /9-Cymene Limonene y-Terpinene Terpinolene 2-3,8 Menthadiene Carbonyl number (ppm) Dipentene A Dipentene B a-Pinene fi-Pinene < Sulfate Turpentine ■ Dipentene Gum 5 Turpentine 0.10 6.7 0.2 7.0 1.4 41.6 6.5 28.4 3.1 360 3.9 2.9 0.6 0.4 6.4 13.8 29.6 2.2 22.7 1.3 770 95.6 1.6 2.0 54 1.5 0.5 92.4 1.0 0.1 0.7 115 Table 10 Composition of Terpenes as Petroleum Resin Feed Additives 1.7 6.2 0.1 1.1 18.7 1.9 22.1 9.7 29.4 5.8 186 rccu f wi.70/ Steam Cracker Feed (IBP-70°C cut) 40 40 40 40 40 40 Paraffinic Solvent L.V.N. 30 30 30 30 30 30 25 F.C.C. Olefins (IBP-100°C cut) 30 20 20 20 20 20 Carene — 10 . — Limonene 10 Dipentene A 10 — a-Pinene 10 — 30 /3-Pinene 10 Pentadiene 1,3 in Total Feed 7.9 7.9 7.9 7.9 7.9 7.9 Isoprene in Total Feed 9.5 9.5 9.5 9.5 9.5 9.5 Carene in Total Feed — 8.4 0.5 —— Limonene in Total Feed — 0.7 7.9 4.2 __ 35 or-Pinene in Feed ^3-Pinene in Feed 9.6 0.1 9.2 Table 10 (Cont'd) Resin Properties Product 40 Resir^(wt.) 23.6 29.0 31.0 29.1 27.2 36.4 Liquid oligomers (wt.%) 6.0 8.7 9.0 9.9 7.7 5.9 Unreacted Compounds (wt.%) 70.4 61.6 60.0 61.0 65.1 57.7 Product Properties Softening Point 93 97 99 95 93 103 45 Gardener Colour 3 2.5 4 3.5 3.5 3.5 Heat Stability 13+ 13- 13- 12.5 13 13+ Molecular Wt Mn 1435 1345 1300 1900 1470 Mw 3010 3585 3170 2535 4805 Mw/Mn 2.19 2.66 2.48 2.13 3.26 50 Wax Cloud Point °C 50:25:25 80 76 73 68 105 124 40:40:20 120 115 84 142 180° Peel Strength (lb/inch) 2.35 2.45 2.55 2.30 2.25 2.9 Polyken Tack (grams) 850 1000 1100 950 1000 1050 55 Tack Rolling Ball (cm) 4 1.5 3 1.5 3 9 178° Holding Power 35 36 14 16 95 10 15 20 25 30 35 40 45 50 55 Claims (5) Claims 1. A process comprising copolymerising using a Friedel Crafts catalyst (1) a petroleum resin feed comprising C5 olefins and diolefins, C6 olefins and diolefins or a mixture 60 of C5 and C6 olefins and diolefins said feed being obtained from the cracking of petroleum feedstock, and (2) Limonene in the absence of sylvestrene. 60 9 GB 2 032 442 A 9 2, A process comprising copolymerising using a Friedel Crafts catalyst (1) a petroleum diolefins, C6 olefins and diolefins or a mixture of C5 and C6 and diolefins said feed being obtained from the cracking of petroleum feedstock and (2) limonene the petroleum resin feed comprising at least 40 wt.% of the combined weight of limonene and resin feed. 5 3. A process according to claims 1 or claim 2, wherein the polymerisation feed also contains 5 branched olefins, substituted aromatics, tertiary hydrocarbon halide for resin molecular weight contribution control. 4. A process according to any one of the preceding claims, wherein the feed also contains unsaturated C8—C10 aromatics such as styrene, a-methyl styrene, vinyl toluene, indene. 10 5. A resin whenever prepared by a process according to any of the preceding claims. 10 Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained. GB7841463A 1978-10-20 1978-10-20 Petroleum resins Withdrawn GB2032442A (en) Priority Applications (7) Application Number Priority Date Filing Date Title GB7841463A GB2032442A (en) 1978-10-20 1978-10-20 Petroleum resins EP19790302270 EP0011393B1 (en) 1978-10-20 1979-10-19 Petroleum resins and their preparation DK443179A DK156959C (en) 1978-10-20 1979-10-19 PREFERRED EMBARIED SUMMARY OF PREFERRED EMBODIMENTS, SUMMARY OF PREFERRED EMBODIMENTS, WITH , AND A PEARL CRAFT CATALYST JP13504579A JPS5556113A (en) 1978-10-20 1979-10-19 Improved petroleum resin CA000338041A CA1185399A (en) 1978-10-20 1979-10-19 Petroleum resins DE7979302270T DE2964374D1 (en) 1978-10-20 1979-10-19 Petroleum resins and their preparation JP24775187A JPS6399207A (en) 1978-10-20 1987-09-30 Modified petroleum resin Applications Claiming Priority (1) Application Number Priority Date Filing Date Title GB7841463A GB2032442A (en) 1978-10-20 1978-10-20 Petroleum resins Publications (1) Publication Number Publication Date GB2032442A true GB2032442A (en) 1980-05-08 Family ID=10500498 Family Applications (1) Application Number Title Priority Date Filing Date GB7841463A Withdrawn GB2032442A (en) 1978-10-20 1978-10-20 Petroleum resins Country Status (6) Country Link EP (1) EP0011393B1 (en) JP (2) JPS5556113A (en) CA (1) CA1185399A (en) DE (1) DE2964374D1 (en) DK (1) DK156959C (en) GB (1) GB2032442A (en) Cited By (1) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title EP0132291A1 (en) * 1983-06-28 1985-01-30 Exxon Research And Engineering Company Petroleum resins and their production Families Citing this family (7) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title NL8903079A (en) * 1989-12-15 1991-07-01 Stamicarbon RESIN COMPOSITION BASED ON SINGLE AND MULTIPLY OLEFINICALLY SATURATED ALIFATIC HYDROCARBON MONOMERS WITH 5 AND / OR 6 CARBON ATOMS AND TERPS. FR2659972B1 (en) * 1990-03-20 1993-05-21 Norsolor Sa NOVEL PALE HYDROCARBON RESINS WITH AROMATIC CHARACTER AND PROCESS FOR THEIR PREPARATION. JP3783167B2 (en) * 1996-05-28 2006-06-07 新日本石油化学株式会社 Hot melt composition and modified aromatic petroleum resin used therefor US6242550B1 (en) 1999-05-07 2001-06-05 The Goodyear Tire & Rubber Company Polymeric dimethyl- dicyclopentadiene/limonene resin US6228944B1 (en) 1999-06-24 2001-05-08 The Goodyear Tire & Rubber Company Polymeric resinous material derived from limonene, dimethyl-dicyclopentadiene, indene and vinyl toluene US6265478B1 (en) 1999-08-18 2001-07-24 The Goodyear Tire & Rubber Company Polymeric resinous material derived from limonene dicyclopentadiene indene and alpha-methyl styrene CN109337012B (en) * 2018-08-31 2021-07-09 恒河材料科技股份有限公司 Preparation method of phenol modified copolymerized petroleum resin Family Cites Families (4) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title FR840757A (en) * 1937-07-21 1939-05-03 Istituto Per Lo Studio Della G Synthetic rubber JPS4930489A (en) * 1972-07-19 1974-03-18 GB1486211A (en) * 1974-03-04 1977-09-21 Exxon Research Engineering Co Petroleum resins GB1538057A (en) * 1975-08-13 1979-01-10 Exxon Research Engineering Co Petroleum resins 1978 1978-10-20 GB GB7841463A patent/GB2032442A/en not_active Withdrawn 1979 1979-10-19 CA CA000338041A patent/CA1185399A/en not_active Expired 1979-10-19 JP JP13504579A patent/JPS5556113A/en active Granted 1979-10-19 DE DE7979302270T patent/DE2964374D1/en not_active Expired 1979-10-19 EP EP19790302270 patent/EP0011393B1/en not_active Expired 1979-10-19 DK DK443179A patent/DK156959C/en not_active IP Right Cessation 1987 1987-09-30 JP JP24775187A patent/JPS6399207A/en active Pending Cited By (3) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title EP0132291A1 (en) * 1983-06-28 1985-01-30 Exxon Research And Engineering Company Petroleum resins and their production US4824921A (en) * 1983-06-28 1989-04-25 Exxon Research & Engineering Company Petroleum resins and their production US4994516A (en) * 1983-06-28 1991-02-19 Exxon Research & Engineering Company Petroleum resins and their production Also Published As Publication number Publication date EP0011393B1 (en) 1982-12-22 JPS5556113A (en) 1980-04-24 CA1185399A (en) 1985-04-09 JPS6399207A (en) 1988-04-30 DE2964374D1 (en) 1983-01-27 DK156959C (en) 1990-03-05 DK443179A (en) 1980-04-21 EP0011393A1 (en) 1980-05-28 DK156959B (en) 1989-10-23 JPS6327367B2 (en) 1988-06-02 Similar Documents Publication Publication Date Title US4078132A (en) 1978-03-07 "Process for preparing petroleum resins having low softening points and narrow molecular weight ranges" EP0132291B1 (en) 1989-03-22 Petroleum resins and their production US4068062A (en) 1978-01-10 Polymerizing C5 and C6 olefins and diolefins with 3° hydrocarbyl halide to produce narrow molecular weight petroleum resins having low softening points EP0260001B1 (en) 1990-11-22 Hydrogenated petroleum resins and their use in adhesives JP3009460B2 (en) 2000-02-14 Use of resin for tackification US4130701A (en) 1978-12-19 Petroleum resins containing vinyl norbornene or tetrahydroindene EP0318217B1 (en) 1994-05-04 Adhesive formulations US3987123A (en) 1976-10-19 Petroleum resins EP0023061B1 (en) 1985-04-17 Hydrocarbon resins, their preparation and their use in adhesives US4636555A (en) 1987-01-13 Petroleum resins and their production EP0183448B1 (en) 1989-04-05 Hydrocarbon resins EP0013060B1 (en) 1984-02-22 Carene-modified petroleum resins and their production GB2032442A (en) 1980-05-08 Petroleum resins US3966690A (en) 1976-06-29 Modified hydrocarbon resins EP0190868B1 (en) 1988-11-02 Hydrocarbon resins JPS61137829A (en) 1986-06-25 Substituted aromatic hydrocarbon hydrogenated at aromatic nucleus and additive for adhesive produced by use thereof Legal Events Date Code Title Description 1981-02-18 WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)
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