GB1572275A – Acid agent process for producing the same and its use as a curing agent
– Google Patents
GB1572275A – Acid agent process for producing the same and its use as a curing agent
– Google Patents
Acid agent process for producing the same and its use as a curing agent
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Publication number
GB1572275A
GB1572275A
GB36330/77A
GB3633077A
GB1572275A
GB 1572275 A
GB1572275 A
GB 1572275A
GB 36330/77 A
GB36330/77 A
GB 36330/77A
GB 3633077 A
GB3633077 A
GB 3633077A
GB 1572275 A
GB1572275 A
GB 1572275A
Authority
GB
United Kingdom
Prior art keywords
phenol
process according
acid
aldehyde
moles
Prior art date
1976-09-01
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.)
Expired
Application number
GB36330/77A
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.)
VNII SINTETISCHESKICH SMOL
Original Assignee
VNII SINTETISCHESKICH SMOL
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.)
1976-09-01
Filing date
1977-08-31
Publication date
1980-07-30
1977-08-31
Application filed by VNII SINTETISCHESKICH SMOL
filed
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VNII SINTETISCHESKICH SMOL
1980-07-30
Publication of GB1572275A
publication
Critical
patent/GB1572275A/en
Status
Expired
legal-status
Critical
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Classifications
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 – C08G14/00
C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 – C08G14/00 of aldehydes
C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 – C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 – C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
C08G16/0237—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 – C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing sulfur
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
C—CHEMISTRY; METALLURGY
C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
Description
PATENT SPECIFICATION ( 11) 1 572 275
In ( 21) Application No 36330/77 ( 22) Filed 31 Aug1977 ( 19),N( 31) Convention Application No’s 2411951 ( 32) Filed 1 Sep 1976 /’ Soviet Union(SU)2405740 10 Sep 1976 in // ‘ n rq ( 33) Soviet Union (SU) ( 44) Complete Specification Published 30 Jul 1980 ( 51 INT CL 3 C 08 G 8/32 16/02 k / -I /52 Index at Acceptance uos // C 3 R 1 E 2 B 1 N 2 N 1 N 2 Q 2 1 N 2 Q 3 1 N 2 QX 1 N 25 31 A 100 31 C 31 D 100 31 D 1 A 31 D 1 C 31 D 2 A 31 D 2 C 31 D 2 D 31 D 2 E 31 D 4 31 D 5 A C 11 C 12 C 23 C 25 C 28 X C 6 X C 9 N L 2 X ( 72) Inventors: VASILY DMITRIEVICH VALGIN ALEXANDR MAXIMOVICH VASILENKO DMITRY VASILIEVICH VALGIN LJUDMILA ARTEMOVNA ISTRATOVA ( 54) ACID AGENT, PROCESS FOR PRODUCING THE SAME, AND ITS USE AS A CURING AGENT ( 71) We, VSESOJUZNY NAUCHNO-ISSLEDOVATELSKY INSTITUT SINTETICHESKIKH SMOL, a Body Corporate organised under the laws of the Union of Soviet Socialist Republics, of ulitsa Frunze 77, Vladimir, Union of Soviet Socialist Republics, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following 5 statement:
The present invention relates to synthetic oligomers More specifically it relates to processes for producing acid agents of use as catalysts for curing phenolaldehyde resins.
According to the present invention there is provided a process for preparing a waterinsoluble acid agent for use as a catalyst in resin formation, the process comprising continuously reacting at 50 to 150 C in concurrent flow in a flowreactor (a) a hydroxymethyl or a 10 -methylhydroxymethyl derivative of a phenol containing 0 4 to 0 9 moles of hydroxymethyl or a-methylhydroxymethyl groups per mole of phenol and/or (a’) a phenol and an aldehyde in a molar ratio of 1:0 3 to 1:0 9 with (b) a substituted or unsubstituted aromatic sulphonic acid, the molar ratio being one mole of component (a) or (a) with 0 03 to 10 0 moles of component (b) The reaction is carried out as a continuous process in a flow reactor i e a 15 reactor which operates with «ideal displacement» where continuously metered starting components completely displace the reaction product.
By using a flow reactor we have been able to prepare acid agents which have the following advantages over the prior art acid agents; low viscosity (maximum 100 P at 20 C); good acceptor capacity with respect to aldehyde released during the curing of phenol-aldehyde 20 resoles and lower corrosive activity In using such acid agents as catalyst for curing phenoladehyde resins, an improvement of the physical and mechanical properties of cured resins has been noted; thus the ultimate compressive strength was improved by 10-30 %.
Moreover, the cured products had substantially reduced water-and-moisture -absorption capacity ( 200-1000 % lower) Acid agents according to the invention may be used in the 25 leather industry as synthetic tanning agents.
The hydroxymethylphenol or a -methylhydroxymethylphenol can be prepared by catalysed condensation of a phenol and an aldehyde, which phenol and aldehyde can be the same as are reacted with the aromatic sulphonic acid.
Where an aldehyde and a phenol are used to produce an acid agent, the aldehyde may 30 comprise formaldehyde (which can be in the form of formalin or paraformaldehyde), acetaldehyde, benzaldehyde and others such as butyl aldehyde, but preferably formaldehyde and acetaldehyde are used since these are most widely available Longer synthesis times limit the use of aldehydes such as benzaldehyde or butyl aldehyde.
The phenol moiety of the hydroxymethyl or a -methylhydroxymethyl phenol, or the 35 phenol used with an aldehyde, to produce an acid agent may comprise phenol itself or cresol, resorcinol, naphthol and mixtures thereof.
The aromatic sulphonic acid used for the process according to the invention may comprise sulphonic acid such as benzene-, toluene-, phenol-, cresol-, naphthalene-, or naphthol40sulphonic acid or mixtures thereof 40 2 1,572275 2 The acid agent may be modified with various modifier substances such as an alcohol, a nitrogen-containing compound, a metal sulphonate, ortho-phosphoric acid or other appropriate substances which are selected depending on the particular properties to be imparted to the acid agent.
The residence time of the reactants in the reactor is suitably 0 1 to 10 minutes It should not be shorter than the time required for completion of the exothermic reaction involved Failure to comply with this condition can result in a heterogeneous product By appropriately selecting the temperature and reactor size, a time for the completion of the exothermic reaction of 0 1 to 10 minutes, preferably 0 3 to 1 0 minutes can be obtained as the residence 10 time of the reaction mixture in the reactor.
The acid agent formed in a flow reactor as a result of the reaction contains free aromatic sulphonic acid, a phenol-aldehyde novolac, and some sulphonic acid built in to the structure of the phenol-aldehyde oligomer This composition determines the insolubility of the acid agent in water, that is its ability to stratify water-insoluble novalac when diluted with water It also explains the increased reactivity which we have observed Acid agents can be produced 15 by processes embodying the invention with a more ordered structure, that is a narrower molecular weight distribution and which do not contain as impurities high molecular weight branched structures which impart elevated viscosity The starting components are readily available Moreover, the process according to the invention can be conducted with a high 20 output with lower labour and power consumption compared to prior art process.
Addition of up to 50 % by weight of an alcohol to the acid agent reduces its viscosity and improves its reactivity during curing The alcohol may be added either to the reaction mixture in the course of production of the acid agent or to the finished acid agent Where the alcohol is added during the production of the acid agent (i e to the reaction mixture), the stability of the acid agent is also improved Alcohol addition is suitable for an acid agent which is prepared 25 from a hydroxymethyl or a -methylhydroxymethyl phenol in which there are 0 7-0 9 moles of hydroxymethyl a-methylhydroxymethyl groups per mole of phenol, or where the acid agent is prepared by reaction of a phenol and an aldehyde in a molar ratio of 1:0 7 to 1:0 9.
The alcohol can be an aliphatic alcohol or a dimer of polymer thereof and should be a diol or polyol Preferred aliphatic monomeric diols comprise ethylene and propylene glycols, and 30 butane diols Examples of oligomeric diols include polymerization products of alkylene oxides, including diethylene-triethylene and polyethylene glycols with molecular weight up to 500 An example of a polyol which may be used is glycerin.
To reduce corrosive activity and improve the acceptor capacity with respect to aldehydereleased during the curing of-phenol-aldehyde resins, a maximum 0 8 moles of a nitrogen 35 containing amine or amide compound can be incorporated in the acid agent The nitrogencontaining compound may be added either to the reaction mixture during the production of acid agent, or to the finished acid agent.
During the production of an acid agent by a process according to the invention, bases or salts of weak acids of metals forming metal sulphonates with an aromatic sulphonic acid may 40 be added to the reaction mixture, generally in an amount up to a maximum of 0 1 mole per mole of sulphonic acid This neutralization step permits further reduction of the corrosive activity of the acid agent Suitable neutralizing substances comprise oxides, hydroxides, carbonates and borates (i e bases and salts of weak acids) of metals such as barium, calcium, copper, silver, zinc, tin, iron Phenol-aldehyde resins cured with an acid agent containing 45 metal sulphonates usually exhibit lowered water a nd moisture absorption.
To impart additional fire resistance to polymeric combpositions after curing, up to 20 % by weight of orthophosphoric or boric acid can be added to the acid agent according to the invention The ortho-phosphoric or boric acid is generally added to the finished acid agent, but in a number of applications the modifier acid may however be added during the 50 production of the acid agent In this case it is preferred to use an aqueous solution of ortho-phosphoric acid as solvent for the sulphonic acid.
The quantity of the above-mentioned additives incorporated in the acid agent should be consistent with its insolubility in water, liquid state, an acid number from 10 to 300 mg KOH, preferably from 20 to 150 mg KOH, 55 g g and a maximum water content of 35 % by weight.
To reduce corrosive activity and improve the reactivity of an acid agent according to the invention, a part of the water can be removed from the product by vacuum drying, provided that the viscosity of the resultant acid agent does not exceed 100 P at 20 C To the same end, 60 use can be made in the preparation of a hydroxymethyl derivative of a phenol from which a part of water has been removed, e g by vacuum drying, the viscosity not exceeding 100 P at C.
The invention will be illustrated by the following Examples which are tabulated.
Table 1 gives examples of the preparation of hydroxymethyl derivatives of phenol 65 1,572,275 Tables 2 and 3 give examples of the preparation of acid agents.
The starting components, in accordance with the formulations, were fed by means of a metering pump, to the reactor, in which the residence time of reaction mixture was maintained within the range from 0 1 to 10 minutes and the temperature within the range from 50 5 to 150 C.
In all the examples an aromatic sulphonic acid was used in the form of a saturated aqueous or aliphatic alcohol solution Hydroxymethyl derivatives of phenol, phenol and an aldehyde were fed to a flow reactor in liquid state.
The following terms and abbreviations are used in Tables 1, 2 and 3:
Formalin aqueous solution of formaldehyde ( 37 %); 10 tricresol mixture of isomeric cresols; BSA benzene sulphonic acid; PSA mixture of isomeric sulphonic acids; NLSA 2-naphthol -7-sulphonic acid; NNSA mixture of isomeric naphthalene sulphonic acids; 15 TSA toluene sulphonic acid; PG propylene glycol; EG ethylene glycol; DEG diethylene glycol; PRG 400 polyethylene glycol (Mol wt 400); 20 GL glycerin; BD 1,4 -butane diol; DTEG dimethyl tetraethylene glycol.
Preparation of hydroxymethyl Derivatives of Phenol Table 1
Example Phenol Phenolic corn Formalin Aldehy Alkaline Tempera Condensa Water con Viscosity No Moles ponents ( 37 %) de compo catalyst, ture, C tion time, tent, % at 20 C moles moles nents, moles h c P moles 1 2 3 4 5 6 7 8 9 10 I 1,0 2 1,0 3 1,0 4 1,0 1,0 6 1,0 7 8 1,0 9 1,0 0,5 M-cresol 0,5 P-cresol 0,4 0,6 0,8 0,8 1,0 2,0 0,8 0,25 0,5 0,6 0,4 resorcinol 0,6 0,5 paraformaldehyde 90 % 0,27 acetaldehyde 0,035 Na OH 80 0,018 Ba(OH)2 80 0,018 Ba(OH)2 80 0,035 Na OH 80 0,018 Ba(OH)2 80 0,035 Ba(OH)2 85 0,035 Na OH 75 0,018 Ba(OH)2 80 0,018 Ba(OH)2 95 0,018 Ba(OH)2 80 0,25 I I I I I 0,5 14 I 15,91 21,59 25,54 26,46 28,80 14,20 24,47 11,38 18,58 17,29 -4 16 19 24 27 2400 285 Table 1 (cont’d) 0,375 m-cresol 11 0,375 p-cresol 0,25 resorcinol 12 1,0 13 0,625 tricresol 0,375 resorcinol 14 1,0 0,6 0,6 1,5 0,035 Na OH 75 0,018 Ba(OH)2 80 0,625 acetaldehyde ( 75 % 0/) 0,013 Ba(OH)2 75 0,020 Ba(OH)i 2 80 0,5 I 2,5 20,65 0,75 7,36 35,82 107 320 C.A -A Preparation of Acid Agent from Aryl Sulphonic Acid and hydroxymethyl Derivative of Phenol Examp Aromatic sulpho Hydroxymethyl Neutralizer, Nitrogen Diluent, % Water Acid Viscosity le No nic acid, moles derivatives of moles containing by weight content, number at 20 C, phenol from the compound, % by mg KOH/g Examples of moles weight Table 1
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