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GB1586650A - L trialkoxy silanes - Google Patents

L trialkoxy silanes Download PDF

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Publication number
GB1586650A
GB1586650A GB17102/78A GB1710278A GB1586650A GB 1586650 A GB1586650 A GB 1586650A GB 17102/78 A GB17102/78 A GB 17102/78A GB 1710278 A GB1710278 A GB 1710278A GB 1586650 A GB1586650 A GB 1586650A
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reaction
initiator
copolymer
temperature
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Dynamit Nobel AG
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    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Description

(54) A PROCESS FOR COPOLYMERISING MALEIC ACID ANHYDRIDE AND VINYL TRIALKOXY SILANES (71) WE, DYNAMIT NOBEL AKTI ENGESELLSCHAFT, a German Company of 521 Troisdorf bez Kiln, postfach 1209, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which is is to be performed, to be particularly described in and by the following statement: This invention relates to a process for copolymerising maleic acid anhydride and vinyl trialkoxy silanes.
Some processes for the copolymerisation of maleic acid anhydride with vinyl triethoxy silane are known (Ind. Eng.
Chem. 45 (1953), No. 2, pages 367 to 374).
The polymerisation reactions on which these processees are based are carried out in solution, for example in dioxane or toluene. However the polymerisation times are relatively long (French Patent No. 1,572,851), i.e. the copolymerisation velocities are relatively low.
It has been found that the velocity of copolymerisation of maleic acid anhydride with vinyl trialkoxy silanes increases to a considerable extent in the absence of a solvent. However this gives rise to difficulties when it comes to dissipating the heat of polymerisation. Although it is possible by using an excess of vinyl trialkoxy silane (of for example 1 8 molar), to control the copolymerisation reaction in a 1 litre laboratory flask, the copolymerisation reaction usually cannot be satisfactorily controlled on even the 10 litre scale.
According to the present invention there is provided a process for copolymerising maleic acid anhydride and a vinyl trialkoxy silane which comprises forming a mixture of maleic acid anhydride and the vinyl trialkoxy silane and adding thereto a copolymerisation initiator to promote reaction to form the desired copolymer, the initiator being added continuously or in portions to the mixture whilst the copolymerisation reaction is proceeding.
The mixture preferably has the maleic acid anhydride and vinyl trialkoxy silane present in a molar ratio of from 1:1 to 1:3, more preferably 1 :1 1 to 1:20 and in a particularly preferred embodiment in a ratio of from 1: 1 1 to l:1'9 g, i.e.
the silane is preferably used in excess.
The alkoxy groups of the vinyl trialkoxy silane, which may be the same or different, preferably have up to 8 carbon atoms, and more preferably up to 6 carbon atoms.
They may be, for example, ethoxy groups or propoxy groups.
It is particularly preferred to carry out the polymerisation reaction in the absence of solvents or diluents, because it has been found that, even in the absence of solvents or diluents, addition of the initiator (catalyst) in portions or continuously enables the polymerisation velocity to be effectively controlled. However, it is possible, although not preferred, to add up to 30% by weight and generally up to 20% by weight, based on the starting materials, of solvents or diluents. In that case, the solvents used may be for example aromatic solvents, such as xylene, methyl benzene, acetone and tetrahydrofuran.
Conventional polymerisation catalysts may be used as initiators, for example peroxides or azo compounds. It is preferred to use dicumyl peroxide, butyl perbenzoate or bis-(l, 3-t-butyl-peroxyisopropyl)-benzene, although in general it is possible to use diacyl peroxides, dialkyl peroxides, peresters and azo compounds, among which particular reference is made to dibenzoyl peroxide, methyl benzoyl peroxide, azoisobutyrodinitrile and di-tbutyl peroxide.
The quantity in which the initiator is used preferably amounts to from 0 02 to 5% by weight, and more preferably from 0 1 to 2% by weight, based on the weight of the monomer mixture; the actual quantity used depends upon the activity of the catalyst. Where the catalyst is added in portions, it is preferred to add at least 2 to 3 portions, but no more than 10 to 15 portions, i.e. preferably from 2 to 15 portions and more preferably from 3 to 10 portions. It is preferred to add the initiator in the form of a solution in the vinyl trialkoxy silane.
The polymerisation temperature preferably does not exceed 150 or 1600C, so that, depending on the activity of the catalyst, temperatures of from 50 to 145"C are possible, although temperatures of from 100 to 140"C are generally preferred.
The favourable polymerisation temperature for the particular initiator is best determined by preliminary tests.
Polymerisation, working up and storage are preferably carried out in the absence of moisture.
The pressure at which the process is carried out is preferably from normal pressure to 5 to 10 bars excess pressure, although it may even amount to as much as 50 bars.
The vinyl trialkoxy silanes used preferably contain from 1 to 8 carbon atoms in the alkoxy group, which may be primary or, optionally, secondary. Particularly preferred alkoxy groups are ethoxy groups and also propoxy groups.
The choice of the monomer, vinyl trialkoxy silane, is governed by the purpose for which the copolymer is to be used.
The initiator may be selected accordingly by tests. If the copolymer is to be used for coating silicate-containing substrates for example, the vinyl trialkoxy silane used is preferably a readily hydrolysable silane, for example vinyl triethoxy silane.
The products are alternating copolymers in which the maleic acid anhydride unit is attached on both sides to vinyl trialkoxy silane units with the anhydride group substantially intact. The silane is generally present in a slight excess.
The molecular weight of the copolymers produced by the process of the invention is preferably from 300 to 8000, polymers having molecular weights upwards of 1000 and, more particularly, in the range from 3000 to 6000 being especially preferred.
The polymers produced are generally insoluble in water and soluble in weakly alkaline or weakly ammoniacal solutions which may also be acidified, particularly in a 0 5 to 5% by weight solution of ammonia in water, and in inert organic solvents, for example aromatic solvents such as xylene or toluene, ketones such as acetone, and cyclic ethers such as tetrahydrofuran.
As mentioned above, it is preferred to use an excess of monomeric vinyl trialkoxy silane. On completion of polymerisation, the excess silane may be directly distilled off for example under reduced pressure or even in vacuo, while stirring with substantially no crosslinking occurring. The copolymer may thus be discharged from the reaction vessel by pumping, for example onto a cooled metal belt. By contrast, if the initiator used for the copolymerisation of maleic acid anhydride with the vinyl trialkoxy silane is not added gradually, i.e. in portions or continuously, partial crosslinking may take place so that the copolymer cannot readily be discharged from the reaction vessel.
It has also been found that the copolymer can be obtained in powder form by discharging the product mixture including the crude copolymer while stirring into aliphatic and/or cycloaliphatic hydrocarbons, for example with boiling ranges from 60 to 2000C. To this end, the aliphatic or cycloaliphatic hydrocarbon may be stirred at temperatures below 50"C.
A fine-grained copolymer is generally obtained in this way. This measure also generally provides for the formation of a copolymer which is distinguished by its particularly clear, clouding-free solubility, apparently because impurities and low molecular weight fractions do not precipitate but remain in solution in the hydrocarbon.
Working up may also be carried out with advantage by distilling off the excess vinyl trialkoxy silane, which surprisingly does not damage the copolymer, and subsequently removing the copolymer. In this case, working up is preferably carried ont in vacuo at temperatures of up to about 150"C and more particularly at temperatures of from 100 to 1500C. The copolymer may be removed for example by pumping off or running off. The copolymer may be left to harden, for example on a cooling plate which may optionally be in motion.
In order to obtain a linear polymerisation velocity, it is preferred to dissolve the maleic acid anhydride in 1 1 to 1'9 times the molar quantity of vinyl triethoxy silane, to heat the resulting solution to the polymerisation temperature and then to add the initiator gradually, that is either continuously or in portions. The type of initiator used is governed by the polymerisation temperature and by the constitution of the vinyl trialkoxy silane.
In the case of vinyl triethoxy silane, dicumyl peroxide is distinguished by its particular activity and selectivity, particularly at temperatures of from 120 to 145"C and more especially at temperatures of from 130 to 140"C. For metering purposes, the dicumyl peroxide is best dissolved in vinly triethoxy silane.
The same applies to other initiators having similar half-life periods, particularly t-butyl perbenzoate, bis- (1, 3-t-butyl peroxy-isopropyl)-benzene.
The following Examples illustrate the invention.
Example I (Comparison) In a 1 litre three-necked flask equipped with a stirrer, an inlet tube for nitrogen and a reflux condenser, 147 g of maleic acid anhydride were dissolved under nitrogen in 510 g of vinyl triethoxy silane which had been distilled in the absence of moisture at a temperature of 70"C. 3.9 g of dicumyl peroxide were then added to the solution, followed by heating to 135"C.
A vigorous reaction began and the temperature rose to 155"C without further heating. In order to prevent the temperature from increasing any further, the reaction vessel had to be cooled with ice water. After 30 minutes, the vigorous reaction abated; the reaction as a whole was completed after heating for 3 hours at 135"C. After removal of excess vinyl triethoxy silane by distillation, there remained 453 g of copolymer. The copolymer had a relative viscosity of 1 1 (1 % in ethanol).
Example 2 147 g of maleic acid anhydride were dissolved in 460 g of vinyl triethoxy silane in the same way as in Example 1, after which the resulting solution was heated to 135"C. An initiator solution of 3.9 g of dicumyl peroxide in 50 g of vinyl triethoxy silane was then added dropwise in such a way that the reaction temperature stayed between 135 and 140"C. The initiator solution was added over a period of 1 hour, and thereafter the reaction temperature was kept at 135"C for 2 hours. The further procedure was then as in Example 1. 450 g of copolymer with a relative viscosity of 1 1 (1 % in ethanol) were obtained.
Example 3 The procedure was as in Example 2, except that the excess vinyl triethoxy silane was not distilled off. Instead the copolymer containing the excess vinyl triethoxy silane was cooled to 80"C and slowly added dropwise with stirring to 1800 g of petroleum ether (b.p. 60"C) which was maintained by cooling at a temperature of +5 0C.
The copolymer precipitated in the form of a fine powder. After filtration in a pressure filter and drying in vacuo, 405 g of finely powdered copolymer were obtained. The copolymer formed a completely clear solution in 1 % by weight aqueous ammonia. The excess vinyl triethoxy silane was separated from the petroleum ether by distillation, with 45 g of a viscous oil consisting of low molecular weight copolymer being left in the residue.
Example 4 (Comparison) In a 10 litre capacity, heat-recirculating, electronically temperature-controlled, steel autoclave heated by water under pressure, 1'07 kg of maleic acid anhydride were dissolved at 80"C in 3.55 kg of vinyl triethoxy silane. 19 6 g of dicumyl peroxide were then added, followed by heating to 135 0C. After 10 minutes, the reaction temperature began rising, and over a period of 5 minutes increased to more than 1600C despite the fact the electronic temperature control system came into operation and the reaction mixture was cooled. Only by pumping cold water (14"C) into the pressurised autoclave heating system could the reaction temperature be brought below 135"C. The reaction was over after only 40 minutes. Removal of the excess vinyl triethoxy silane by distillation left 3.3 kg of copolymer which, however, could not be removed from the autoclave simply by pumping.
Example 5 In a 10 litre capacity steel autoclave equipped in the same way as in Example 4, 1 07 kg of maleic acid anhydride were dissolved in 3'2 kg of vinyl triethoxy silane and the resulting solution was heated to 135"C. The internal pressure amounted to around 1 bar. A catalyst solution of l9'6 g of dicumyl peroxide in 350 g of vinyl triethoxy silane was prepared and stored, and 35 g of this catalyst solution were pumped into the autoclave. The internal temperature increased to a maximum of l36'50C and was reduced to 135"C over a period of 10 minutes by the electronic temperature control system.
Thereafter 9 batches of 35 g of catalyst solution were pumped in at 10 minute intervals. The maximum internal temperature amounted to 136 Soc with each input of the catalyst solution. The reaction was continued for 2 hours after the catalyst solution had been added by heating to 135"C, and then it was terminated. The excess vinyl triethoxy silane was distillated off in vacuo. The residue, consisting of the polymer, was pumped from the autoclave at 1200C and solidified on a cooled plate to form a solid mass. 3.3 kg of copolymer were obtained.
Example 6 (Comparison) In a 500 cc capacity three-necked flask equipped with a stirrer, an inlet, tube for nitrogen and a reflux condenser, 34'8 g of maleic acid anhydride were dissolved under nitrogen with stirring in 140 g of vinyl tripropoxy silane in the absence of moisture at a temperature of 110 C.
092 g of dicumyl peroxide were then added in a single portion, followed by heating to 135"C. When this temperature was reached, a vigorous reaction began, the temperature rising in 15 minutes to a level of 148"C. The temperature is brought to 135"C by cooling with cold water. After 20 minutes, the reaction abated and excess vinyl tripropoxy silane was distilled off.
128 g of copolymer were obtained.
Example 7 The procedure was as in Example 6, except that, after heating to 135"C, the initiator was added in 4 portions of 0.23 g at intervals of 10 minutes at a temperature of 135 C, the temperature rising to only 138"C without the reaction mixture having to be cooled with water. After the initiator had been added, the reaction was continued by heating at 135"C for 3 hours, and then it was terminated. Removal of the excess vinyl propoxy silane by distillation left 128 g of copolymer.
Example 8 (Comparison) As in Example 6, 27 g of maleic acid anhydride were dissolved in 135 g of vinyl tributoxy silane at a temperature of 110"C.
Thereafter 0'71 g of dicumyl peroxide were added and the reaction mixture was heated to 135 C. The temperature rose to 1550C over a period of 30 minutes, and was reduced to 135"C by cooling.
The reaction was terminated after 3 hours at that temperature. Removal of excess vinyl tributoxy silane by distillation yielded 125 g of copolymer.
Example 9 The procedure was as in Example 8, except that the initiator was added in portions of 0 18 g at intervals of 15 minutes at a temperature of 135"C. The temperature rose to a maximum of 137"C.
Thereafter the reaction was terminated after maintaining a temperature of 135"C for 3 hours. Removal of the excess vinyl tributoxy silane by distillation yielded 125 g of copolymer.
Example 10 The procedure was as in Example 5, except that the 10 litre steel autoclave was replaced by a 30 litre steel autoclave, with 3 21 kg of maleic acid anhydride and 9 6 kg of vinyl triethoxy silane being used.
An anchor stirrer (200 rpm) was used to stir the reactants. A solution of 58'8 g of dicumyl peroxide in 1'05 kg of vinyl triethoxy silane was used as initiator. This solution was pumped into the autoclave in 12 portions at 10 minute intervals at a temperature of 135"C. In this case, too, the internal temperature did not exceed 136-5 C. Further, no difficulties were encountered in dissipating the heat of reaction by means of the electronic temperature control device. The reaction mixture was worked up in the same way as in Example 5.
The same results were obtained when t-butyl perbenzoate or bis-(1,3-t-butylperoxy-isopropyl)-benzene were used as initiator instead of dicumyl peroxide.
Apart from the fact that it is simple to carry out, the process according to the invention as exemplified above has been found to yield a high-quality product which can be satisfactorily dissolved without clouding in aqueous-alkaline medium.
In addition, the maleic acid component is completely reacted, which is surprising since in the case of substantially alternating copolymerisation reactions copolymerisation generally takes place spontaneously.
WHAT WE CLAIM IS: 1. A process for copolymerising maleic acid anhydride and a vinyl trialkoxy silane which comprises forming a mixture of maleic acid anhydride and the vinyl trialkoxy silane and adding thereto a copolymerisation initiator to promote reaction to form the desired copolymer the initiator being added continuously or in portions to the mixture whilst the copolymerisation reaction is proceeding.
2. A process according to claim 1 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1:1 to 1:3.
3. A process according to claim 2 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1:l'1 to 1:20.
4. A process according to claim 3 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1: 1 1 to 1:1'9.
5. A process according to any one of the preceding claims wherein the alkoxy group of the vinyl trialkoxy silane contains from 1 to 8 carbon atoms.
6. A process according to claim 5 wherein the alkoxy group of the vinyl trialkoxy silane contains from 1 to 6 carbon atoms.
7. A process according to claim 6 wherein the alkoxy group is ethoxy or propoxy.
8. A process according to any one of the preceding claims wherein the total amount of initiator added is from 002 to 5% by weight, based on the weight of the mixture.
9. A process according to claim 8 wherein the total amount of initiator added is from 0'1 to 2% by weight, based on the weight of the mixture.
10. A process according to any one of the preceding claims wherein the initiator is added in the form of a solution in the vinyl trialkoxy si1ane.
11. A process according to any one of the preceding claims wherein the initiator is added in from 2 to 15 portions.
12. A process according to claim 11 wherein the initiator is added in from 3 to 10 portions.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (31)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    135"C by cooling with cold water. After 20 minutes, the reaction abated and excess vinyl tripropoxy silane was distilled off.
    128 g of copolymer were obtained.
    Example 7 The procedure was as in Example 6, except that, after heating to 135"C, the initiator was added in 4 portions of 0.23 g at intervals of 10 minutes at a temperature of 135 C, the temperature rising to only 138"C without the reaction mixture having to be cooled with water. After the initiator had been added, the reaction was continued by heating at 135"C for 3 hours, and then it was terminated. Removal of the excess vinyl propoxy silane by distillation left 128 g of copolymer.
    Example 8 (Comparison) As in Example 6, 27 g of maleic acid anhydride were dissolved in 135 g of vinyl tributoxy silane at a temperature of 110"C.
    Thereafter 0'71 g of dicumyl peroxide were added and the reaction mixture was heated to 135 C. The temperature rose to 1550C over a period of 30 minutes, and was reduced to 135"C by cooling.
    The reaction was terminated after 3 hours at that temperature. Removal of excess vinyl tributoxy silane by distillation yielded 125 g of copolymer.
    Example 9 The procedure was as in Example 8, except that the initiator was added in portions of 0 18 g at intervals of 15 minutes at a temperature of 135"C. The temperature rose to a maximum of 137"C.
    Thereafter the reaction was terminated after maintaining a temperature of 135"C for 3 hours. Removal of the excess vinyl tributoxy silane by distillation yielded 125 g of copolymer.
    Example 10 The procedure was as in Example 5, except that the 10 litre steel autoclave was replaced by a 30 litre steel autoclave, with 3 21 kg of maleic acid anhydride and 9 6 kg of vinyl triethoxy silane being used.
    An anchor stirrer (200 rpm) was used to stir the reactants. A solution of 58'8 g of dicumyl peroxide in 1'05 kg of vinyl triethoxy silane was used as initiator. This solution was pumped into the autoclave in 12 portions at 10 minute intervals at a temperature of 135"C. In this case, too, the internal temperature did not exceed 136-5 C. Further, no difficulties were encountered in dissipating the heat of reaction by means of the electronic temperature control device. The reaction mixture was worked up in the same way as in Example 5.
    The same results were obtained when t-butyl perbenzoate or bis-(1,3-t-butylperoxy-isopropyl)-benzene were used as initiator instead of dicumyl peroxide.
    Apart from the fact that it is simple to carry out, the process according to the invention as exemplified above has been found to yield a high-quality product which can be satisfactorily dissolved without clouding in aqueous-alkaline medium.
    In addition, the maleic acid component is completely reacted, which is surprising since in the case of substantially alternating copolymerisation reactions copolymerisation generally takes place spontaneously.
    WHAT WE CLAIM IS: 1. A process for copolymerising maleic acid anhydride and a vinyl trialkoxy silane which comprises forming a mixture of maleic acid anhydride and the vinyl trialkoxy silane and adding thereto a copolymerisation initiator to promote reaction to form the desired copolymer the initiator being added continuously or in portions to the mixture whilst the copolymerisation reaction is proceeding.
  2. 2. A process according to claim 1 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1:1 to 1:3.
  3. 3. A process according to claim 2 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1:l'1 to 1:20.
  4. 4. A process according to claim 3 wherein the mixture comprises maleic acid anhydride and vinyl trialkoxy silane in a molar ratio of from 1: 1 1 to 1:1'9.
  5. 5. A process according to any one of the preceding claims wherein the alkoxy group of the vinyl trialkoxy silane contains from 1 to 8 carbon atoms.
  6. 6. A process according to claim 5 wherein the alkoxy group of the vinyl trialkoxy silane contains from 1 to 6 carbon atoms.
  7. 7. A process according to claim 6 wherein the alkoxy group is ethoxy or propoxy.
  8. 8. A process according to any one of the preceding claims wherein the total amount of initiator added is from 002 to 5% by weight, based on the weight of the mixture.
  9. 9. A process according to claim 8 wherein the total amount of initiator added is from 0'1 to 2% by weight, based on the weight of the mixture.
  10. 10. A process according to any one of the preceding claims wherein the initiator is added in the form of a solution in the vinyl trialkoxy si1ane.
  11. 11. A process according to any one of the preceding claims wherein the initiator is added in from 2 to 15 portions.
  12. 12. A process according to claim 11 wherein the initiator is added in from 3 to 10 portions.
  13. 13. A process according to any one of
    the preceding claims wherein the initiator is a peroxide.
  14. 14. A process according to claim 13 wherein the initiator is dicumyl peroxide, butyl perbenzoate or bis-(1,3-t-butylperoxy-isopropyl)-benzene.
  15. 15. A process according to any one of the preceding claims wherein the reaction is carried out at an excess pressure of up to 10 bars.
  16. 16. A process according to any one of the preceding claims wherein the reaction is carried out at a temperature which is not greater than 1600C.
  17. 17. A process according to claim 16 wherein the reaction is carried out at a temperature of from 50 to 145 0C.
  18. 18. A process according to claim 17 wherein the reaction is carried out at a temperature of from 100 to 140"C.
  19. 19. A process according to any one of the preceding claims wherein the reaction is carried out in a solvent or diluent.
  20. 20. A process according to any one of the preceding claims which includes the additional step of separating the copolymer from the product mixture.
  21. 21. A process according to claim 20 wherein the copolymer is separated by distilling excess vinyl trialkoxy silane from the product mixture.
  22. 22. A process according to claim 21 wherein the distillation is carried out at reduced pressure.
  23. 23. A process according to claim 21 or 22 wherein the copolymer is removed from the reaction vessel in liquid form and cooled to solidify the same.
  24. 24. A process according to claim 20 wherein the copolymer is separated by pouring the product mixture, with stirring into an aliphatic hydrocarbon and/or a cycloaliphatic hydrocarbon to form a mixture of hydrocarbon and powder-form copolymer, and separating the powder from the mixture.
  25. 25. A process according to claim 24 wherein the hydrocarbon has a boiling point of from 60 to 200"C.
  26. 26. A process according to claim 24 or 25 wherein the hydrocarbon is at a temperature which is less than 50"C.
  27. 27. A process according to claim 1 substantially as described in Example 2, 3, 5, 7, 9 or 10.
  28. 28. A process according to claim 1 substantially as hereinbefore described.
  29. 29. A copolymer of maleic acid anhydride and a vinyl trialkoxy silane whenever produced by the process according to any one of the preceding claims.
  30. 30. A copolymer according to claim 29 having a molecular weight of from 300 to 8000.
  31. 31. A copolymer according to claim 30 having a molecular weight of from 3000 to 6000.
GB17102/78A 1977-04-30 1978-04-28 L trialkoxy silanes Expired GB1586650A (en)

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DE19772719458 DE2719458A1 (en) 1977-04-30 1977-04-30 PRODUCTION OF COPOLYMERS FROM MALEIC ACID ANHYDRIDE AND VINYLTRIAL COXYSILANES

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CA (1) CA1104295A (en)
DE (1) DE2719458A1 (en)
FR (1) FR2388838A1 (en)
GB (1) GB1586650A (en)
IT (1) IT1104101B (en)
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SE (1) SE7804856L (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5518770A (en) * 1995-02-23 1996-05-21 Betz Laboratories, Inc. Methods and compositions for pretreatment of metals
AU711097B2 (en) * 1995-05-08 1999-10-07 Nalco Chemical Company Dadmac/vinyl trialkoxysilane copolymers and their use in wastewater treatment

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2560316Y2 (en) * 1992-12-25 1998-01-21 株式会社河合楽器製作所 Acoustic reflector device
JPH0733150U (en) * 1993-12-07 1995-06-20 晃 近藤 Pillow for chair

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* Cited by examiner, † Cited by third party
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US3560589A (en) * 1967-07-12 1971-02-02 Shinetsu Chemical Co Epoxy resin containing a vinyl alkoxysilane-ethylenically unsaturated acid anhydride copolymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5518770A (en) * 1995-02-23 1996-05-21 Betz Laboratories, Inc. Methods and compositions for pretreatment of metals
US5612421A (en) * 1995-02-23 1997-03-18 Betzdearborn Inc. Methods and compositions for pretreatment of metals
AU711097B2 (en) * 1995-05-08 1999-10-07 Nalco Chemical Company Dadmac/vinyl trialkoxysilane copolymers and their use in wastewater treatment

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JPS53136092A (en) 1978-11-28
FR2388838A1 (en) 1978-11-24
IT7849140A0 (en) 1978-04-28
DE2719458A1 (en) 1978-11-02
SE7804856L (en) 1978-10-31
CA1104295A (en) 1981-06-30
NL7804661A (en) 1978-11-01
BE866525A (en) 1978-08-14
IT1104101B (en) 1985-10-14
JPS6147849B2 (en) 1986-10-21

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