DE1930673A1 - Process for the production of solid methyl vinyl ether / maleic acid copolymers and their use - Google Patents

Description

Imperial Chemical Industries Linited London / Great Britain

Process for the production of solid methyl vinyl ether / maleic acid copolymers and their use

The invention relates to a process for the production of copolymers from methyl vinyl ether and Maleic acid in solid form, which dissolves or swells quickly in cold water, and the solid forms it produces Mixed polymers.

Mixed polymers of methyl vinyl ether and maleic anhydride are valued thickening, suspending, binding and film-forming substances. When these copolymers are suspended in water, the anhydride ring is hydrated to form free acid groups _# and the resulting

909881 / U57

8AO ORIGINAL

(A,

Methyl vinyl ether / Malelnslttxv mixed polymers dissolve in Water. However, this process is slow at room temperature and may take 24 to 48 hours. By being hit the suspension of methyl vinyl ether / maleic anhydride copolymers in water at about 90 ° C it is possible to prepare solutions in 20 minutes. However, this lengthens Heating level, the duration of the preparation and after the vessels, that need to be stirred and heated, and auxiliary equipment necessary. When the interpolymer is hydrolyzed to the free acid form and isolated as a solid, the solid can be quickly dissolved in water. A solid methylvinyl maleic acid copolymer can by dissolving methyl vinyl ether / maleic anhydride copolymers in water and evaporating the solution to dryness, but this method is expensive and difficult to apply to high molecular weight interpolymers and the product is obtained in a form which is difficult to isolate. The "free acid" in solid form can also be caused by exposure to methyl vinyl ether / Maleic anhydride copolymers can be produced in a humid atmosphere at room temperature, but this can Procedure takes several months and is difficult to reproduce.

The object of the invention is to provide an improved process for the production of solid methyl vinyl ether / maleic

909881/1 .A 57

BATH ORIGINAL

Acid mixed polymer to be provided.

In accordance with the invention, a solid copolymer of methyl vinyl ether and maleic acid is produced by a process produced in which a water-soluble or water-swellable methyl vinyl ether / maleic anhydride copolymer with 10 to 33% water, based on the dish of the mixed polymer optionally mixed in the presence of an acidic or basic catalyst and the mixture for a while is heated sufficient to effect hydrolysis of at least some of the anhydride groups. The required Heating time can vary from 30 minutes to about 30 days depending on the temperature, being high Temperatures favor lower reaction times. The product can then be ground to a fine powder or be rubbed.

It is expressly stated that in this context the term "methyl vinyl ether / maleic anhydride mixed polymer" not only including those composed of methyl vinyl ether and maleic anhydride alone Mixed polymers, but also including mixed polymers of methyl vinyl ether, maleic anhydride and other monomers is used. So can

909881/1457

BATH ORIGINAL

fast dissolving or fast swelling solid copolymers from mixed polymers of methyl vinyl ether and maleic anhydride including inclusion

(a) an unsaturated surfactant such as described in British patent application 43 106/66,

(b) a fatty vinylidene as described in British patent application 32 935/67, or

(c) a crosslinking agent such as an epoxy group containing compound as described in British Patent 1,069,637 or an unsaturated group and a hydroxyl group-containing compound as described in British Patent Application 52,703/67 will.

By the method according to the invention, solid copolymers of riethylvinylether / maleic acid can easily which dissolve in Kasser in less than two hours at room temperature, even if the interpolymers are still contain a significant proportion of anhydride groups.

Preferably the amount of water is in the range from 12 to 29 percent by weight of the copolymer. With smaller amounts of water, the hydrolyzed product contains an equilibrium concentration of acid and anhydride groups and requires more than 2 hours to dissolve in water; with

■ »09881/14 57

BATH ORIGINAL

'-JBT-

S "

in large quantities, the product is an extremely tough or extremely sticky mass which is very difficult to grind .

The water can expediently be mixed into the mixed polymer by adding the powdered mixed polymer and a fine spray of water in the desired proportions are dosed into a mixing zone by the Mixed polymers in a long column by means of a fine spray of water, carried by air or nitrogen, is fluidized or by mechanically mixing and / or the required amounts of water and mixed polymer be mechanically ground. The water can be added to the interpolymer before or after the interpolymer is heated.

A defined induction period or initial phase was found after mixing the methyl vinyl ether / maleic acid anhydride mixed polymer with the water, during which very little conversion takes place; the length of this initial phase depends largely on the temperature. At the end of this initial phase, the bulk of the copolymer and water shrinks and becomes partially coherent; the degree of shrinkage is a suitable visual indicator of the course of the reaction.

909881/1457

BATH

In a particularly useful embodiment of the method according to the invention, a water-soluble one Methyl vinyl ether / maleic anhydride copolymer with 23 to 29% water, based on the weight of the copolymer, mixed and heated at a temperature in the range of 38 ° to 48 ° C for 10 to 20 days.

In a further particularly useful embodiment of the process according to the invention, a methyl vinyl ether / maleic anhydride interpolymer is mixed with 12.0 to 14.5% water, based on the weight of the interpolymer, and mixed with stirring in a closed vessel at a temperature in the range of 9O ° heated to 120 ⁰ C for 3 to 20 hours.

The method according to the invention is accelerated by means known to the reaction of a Catalyze anhydride with water. Suitable catalysts include acids and bases, e.g., para-toluenesulfone- acid, sodium hydroxide and pyridine. The amount of catalyst used is preferably less than 1% the total weight of the interpolymer and water.

The amount of water used is generally greater than those required for reaction with all anhydride groups

908181/1457

BATH ORIGINAL

that amount of water, but it is generally not
required to remove them. Should it be required
the free water can be by a normal drying process, preferably at a temperature below
ICXD ⁰ C, removed,

It was found that the product in a
more easily crumbled form is obtained if that for
Water added to initiation of the reaction contains an organic agent which thickens or gels water, for example 0.5 to 1% by weight of the sodium salt of a vinyl / maleic acid copolymer (described in British Patent 1,069,637). It is believed that the thickener keeps the water more evenly distributed in the polymer mass and thus makes the product easier to grind or grind.

A particularly useful aspect of the method according to the invention is that it is carried out simultaneously with
other treatments designed to modify or improve the properties of the methyl vinyl ether / maleic acid copolymer can be used. So
can agents, e.g. substituted hydroxybenzoquinones,
substituted hydroxybenzoates, ethylenediaminetetraacetic acid, 8-hydroxyquinoline and pentachlorophenyl laurate, for

90 9881/1457

ßAD ORIGINAL

improvement of the resistance of the mixed polymer to light, heat, oxidative degradation or biological attack added to the reaction mixture before or after the hydrolysis In the same way, a proportion of e.g. up to 20% of the anhydride groups with an alcohol or a Amine reacted simultaneously with the hydrolysis of the remainder will. The interpolymer can also be mixed with a crosslinking agent such as an epoxy compound or a compound containing many -OH-, -SH- or -NH- groups simultaneously with the method according to the invention for modification or increase the viscosity of the copolymer in aqueous solution. A general the crosslinking agent used is polyethylene glycol.

The methyl vinyl acetate / malelic acid polymeric polymers that are produced by the process according to the invention can be used as textile finishing agents, to change the fluidity or viscosity of aqueous solutions of polymer latices, in suspension polymerisation processes and in the preparation of cosmetics, lubricants, binders, and cosmetics, lubricants, and insecticides , Fungicides and to remove paint.

The invention is explained in more detail below by means of execution examples, with all parts and percentages

909881/1457 "^^ - ^ BADORKaINAL

data are expressed by weight.

example 1

To 10 parts of methyl vinyl ether / maleic anhydride copolymers were added 3 parts of water given; the ingredients were mixed by grinding. The resulting Free flowing powder was sealed in a container heated to 95 ° C. After 10 minutes the Shrink powder mass. After heating at 95 ° C for 2 hours, the container was cooled and the contents, the one hard, brittle mass of methyl vinyl ether / maleic acid copolymers with about half the original volume of the wet interpolymer was lightly ground .

There were 5 parts of the methyl vinyl ether / maleic acid copolymer added to 95 parts of stirred water at room temperature. The mixed polymer dissolved, a clear one Solution in 30 minutes. Da's original interpolymers took more than 24 hours for complete dissolution under identical conditions.

909881/1457

BATH

Example 2

A mixture of 10 parts of methyl vinyl ether / maleic anhydride mixed polymer and 2.5 parts of water containing 0.5% pyridine was ground and the resulting powder was placed in a closed container at 70 ° C. for 21 hours to form a hard, brittle one Heated mass of methyl vinyl ether / maleic acid Miechpolysnereia, which was ground to a powder. 5 Share this · ⁸ Powders dissolved in 95 parts of water at Raumtempera- fctaf in 30 minutes to give a clear Löstang »-

Example 3

There were 275 parts of a 0.2 normal sodium hydroxide solution in 1,300 parts of a methyl vinyl ether / maleic anhydride copolymer ground, and the resulting powder was in a vessel under nitrogen at a Pressure of 3.16 kg / cm (45 psi) completed and at 70 ° C Stirred for 18 hours. The methyl vinyl ether / maleic acid Mlochpolymer, obtained after cooling the vessel was a mixture of fine powder and aggregated Lump. After being ground to a uniform powder, it dissolved in less than a clear solution in water than an hour.

, 90.9881 / 1457

ÖAD ORIGtMAU

Example 4

There was 1 part of a copolymer of methyl vinyl ether and maleic anhydride, which was replaced by 0.045 part of a copolymerized glycidyl methacrylate (such as in British Patent 1,069,637) was crosslinked, dissolved in 80 parts of water at 90.degree. The solution was cooled, neutralized to pH 7 with 4.5 normal sodium hydroxide and with water to one Total amount of 100 parts of a clear gel diluted. 8 parts of this gel with 40 parts (uncrosslinked) Milled methyl vinyl ether / maleic anhydride mill polymer. The resulting mixture was sealed in a vessel; it was held at 95 ° C for 100 minutes and left cool them down. The resulting coherent mass of methyl vinyl ether / maleic acid copolymer was easily ground to a fine powder which dissolved in water at room temperature in 30 minutes.

Example 5

There were 450 parts of a methyl vinyl ether / maleic anhydride mixed polymer in powder form in a vertical cylinder by air-propelled vertically upwards

909881 / U57

BATH

Ji

Directional spray fluidized until 39 parts of water were incorporated into the powder, which was then sealed in a plastic container. The container was held for C 7 days at 6O ^0; the resulting aggregated mass of methyl vinyl ether / maleic acid interpolymer was lightly ground to a powder which dissolved in water at room temperature to form a clear solution in 90 minutes.

Example 6

There were 105 parts of a powdered methyl vinyl ether / maleic anhydride copolymer with 2 parts of a copolymerized hydroxyethyl methacrylate (as described in British patent application 52 7O8 / 67) was crosslinked, as in Example 5 fluidized with 0.02 normal sodium hydroxide solution, to 26.7 parts of the solution Powder were incorporated. The mixture was kept in a sealed container for 2 days at room temperature and then stirred at 40 ° C. for a further 14 days. The resulting aggregated mass of cross-linked »methyl vinyl ether / maleic acid copolymers was ground to a fine powder that showed no tendency to cake on standing.

■ # ·
There were 2.5 parts of the resulting crosslinked methyl

vinyl ether / maleic acid copolymers to 500 parts stirred

9Q9881 / U57

BATH ORIGINAL.

Given water at room temperature. The mixed polymer swelled to a cloudy gel in 15 minutes and was then washed to pH 7 with 4N sodium hydroxide solution neutralized by a clear viscous gel. The original crosslinked copolymer required more than 24 hours to swell to the same extent under identical conditions.

Example 7

There were 6 parts of a powdered methyl vinyl ether / maleic anhydride copolymer with 0.8 parts of a 0.02 normal sodium hydroxide solution as in Example 5 mixed. The mixture was heated in a sealed rotating jar at 120 ° C for 5 hours and allowed to form of methyl vinyl ether / maleic acid mixed polymer in the form of a mixture of powder and spherical grains. The mixture was easily ground to a fine powder which could be dissolved in water at room temperature in 5 minutes solved.

Example 8

There was a jar with 12,712 parts of a powdered methyl vinyl ether / maleic anhydride copolymer

909881/1457

/ it

loaded. The vessel was sealed, rotated and heated at 10O ⁰ C. 1,685 parts of a 0.02 normal sodium hydroxide solution were sprayed into the hot rotating copolymer through a fine spray nozzle. The sealed rotating vessel was held at 100 ° C. for 4 3/4 hours and cooled to form a methyl vinyl ether / maleic acid copolymer in the form of a mixture of powder and spherical grains. The mixture was ground to a fine powder which dissolved in water at room temperature in 1 hour.

Example 9

40 parts of a methyl vinyl ether / maleic anhydride mixed polymer were fluidized as in Example 5 with 0.02 normal sodium hydroxide until 5.3 parts of the solution were incorporated. The mixture was heated in a closed rotating vessel at 100 ^° C. for 5 hours to form a methyl vinyl ether / maleic acid copolymer in the form of a mixture of powder and spherical grains. The mixture was lightly ground to a fine powder which dissolved in water at room temperature in 2 hours.

909881/1457

Example IQ

There were 4 parts of polyethylene glycol in 127 parts a 0.02 normal sodium hydroxide solution. This solution was in 454 parts of an uncrosslinked methyl vinyl ether / Maleic anhydride copolymers mixed in by fluidization as in Example 5. The resulting mixture was Heated in a sealed container at 50 ° C for 16 days and to form a crosslinked methyl vinyl ether / maleic acid copolymer cooled in the form of a hard, brittle mass that was ground to a fine powder.

Ee were 2.5 parts of the resulting crosslinked methyl vinyl ether / maleic acid mixed polymer to 500 parts Added water with stirring at room temperature. The interpolymer dissolved in 20 minutes to form a clear viscous solution, which can be diluted to pH 7 with a 4 normal sodium hydroxide solution to form a clear viscous Solution has been neutralized.

Example 11

1.5 parts of methanol were dissolved in 6.5 parts of water and 4 parts of the solution with 2O parts of a methyl

90988 1 / US7

vinyl ether / malelic anhydride mixed polyBears mixed by grinding. The resulting free-flowing powder was sealed in a container which was kept at 95 ^° C. for 2 hours and allowed to cool. A coherent mousse of partially esterified methyl vinyl ether / maleic acid copolymer was formed and ground to a fine powder that dissolved in water at room temperature in less than 1 hour.

Example 12

Q.4 parts of n-propyl-p-hydroxybenzoate were added to 20 parts of a methyl vinyl ether / maleic anhydride copolymer which had been crosslinked with 0.37 parts of a copolymerized hydroxyethy methacrylate (as described in British patent application 52 708/67) * , The ingredients were mixed together by grinding. This mixture was mixed with a solution of 0.4 parts of disodium complexing acid {ethylenediaminetetraacetic acid} and 5.8 parts of n / 50 sodium hydroxide solution by grinding. The resulting free-flowing powder was sealed in a container which was left to stand for 4 days at room temperature (22 ° C) and then for 1 day at 40 ° C. The accumulated aggregated mass of networked! Methyl vinyl ether / maleic acid blend polymer became a fine powder

90988 1 / US 7

/ fr

ground.

3.1 parts of the resulting crosslinked methyl vinyl ether / maleic acid mixed polymer were added to 300 parts of distilled water at room temperature. After 3.0 minutes, the resulting cloudy swollen gel was neutralized to pH 7 with 4 normal sodium hydroxide solution and distilled water was added to form 500 parts of a clear, viscous gel.

There were 20 parts of methyl vinyl ether / maleic anhydride copolymer, crosslinked with 0.37 parts of mischpol ymerized hydroxyethyl methacrylate, as above described with the exception that the n-propyl p-hydroxybenzoate uiad the disodium salt of the complex-forming Acids have been omitted. From 3.1 parts of the resulting crosslinked methyl vinyl ether / maleic acid copolymers were, as described above, »500 parts of a clear aqueous gels. ^

Samples of each of the two prepared gels were sealed in threaded capped vessels and stored at 70 ° C. The viscosities of these gels were measured in various Z @ ü ± iterv®l] #i using a Brookfieid LVT viscometer measured. After 13 hours at 70 ° C

90988 1/1457

ßAO

the viscosity of the gel prepared from the methyl vinyl ether / maleic acid copolymer containing incorporated n-propyl p-hydroxybenzoate and disodium salt of the complex-forming acid as stabilizers fell from 112,000 centipoise to 70,000 centipoise, while that of the unstabilized gel fell from 104 OOO centipoise had fallen to 10,000 centipoise. After 21 hours at 7O ° C, the viscosities were 22 and 400 cp 7OO centi- poise ψ for the stabilized or unstabilized gel.

90 98 81 / 14S7

Claims (23)

Claims 1. A process for the preparation of a solid copolymer from methyl vinyl ether and maleic acid, thereby characterized in that one is a water-soluble or water-swellable Methyl vinyl ether / maleic anhydride copolymer with 10 to 33% water, based on the weight of the copolymer, mixes and the mixture one for the effect the hydrolysis of at least some of the anhydride groups is heated for sufficient time » 2. Ve £ f © te © s & ffiQoSa ßaGpäagSs l _e net that one laughs 12 him 29 <Sou ₀ = ö Waooos-nafe feo polya »ren, bea © g®a« uf iiao © Q ^ iigMt ioo ». 3. The method according to any one of the preceding claims, thereby g © ls @ Emaeiciuniet _ff . that the reaction of the anhydride mixed p © I; ps © refi with water is acid or base catalyzed * 4. The method according to claim 3 _9, characterized in that the catalyst used is para-Toluolsulfonsäiare, Na- or pyridine 909881 / H57 5. The method according to any one of the preceding claims, characterized in that the catalyst in an amount of less than 1% of the total weight of the Anhydride copolymers and water. 6 · Method according to one of the preceding claims , characterized in that heating is carried out for 30 minutes to 30 days depending on the heating temperature. 7. The method according to any one of the preceding claims, characterized in that the product is ground to a fine powder after heating has ended or grinds. 8. The method according to any one of the preceding claims, characterized in that the water is converted into the methyl vinyl ether / maleic anhydride copolymers mixed in by placing the powdered mixed polymer and a fine water spray in the desired proportion in a mixing zone dosed, the mixed polymer in a long column medium " a fine water spray carried in air or nitrogen fluidized or the necessary water * - and Mixing polymer quantities mechanically and / or grinding. .9 0988 1 / US7 9. The method according to any one of the preceding claims _r, characterized in that the water is added to the anhydride copolymer before or after heating the copolymer. 10. The method according to any one of the preceding claims, characterized in that the methyl vinyl ether / Maleic anhydride copolymers with 23 to 29% water, based on the weight of the copolymer, mixed and heated at a temperature in the range of 38 ° to 48 ° C for 10 to 20 days. 11. The method according to any one of the preceding claims, characterized in that the methyl vinyl ether / Maleic anhydride mill polymers with 12 to 14.5% water, based on the weight of the copolymer, mixed and stirred in a closed vessel at one temperature in the range from 90 ° to 12 ° C for 3 to 20 hours heated. 12. The method according to one of the preceding »claims, characterized in that the water is used in a larger amount than for the reaction with all anhydride groups is required. 809881/1467 bath - 44- - 13. The method according to any one of the preceding claims, characterized in that the remaining free water after the reaction with the anhydride groups by a common drying process removed or not removed. .14. Method according to one of the preceding claims, characterized in that the free water from the copolymer by drying at a temperature below 1OO ° C away. 15. The method according to any one of the preceding claims, characterized in that the water to carry out the reaction with a content of a water thickener or adding gelling organic agents. 16. The method according to any one of the preceding claims, characterized in that the water is used to carry out the reaction with a content of 0.5 to 1% by weight of the Sodium salt of a vinyl / maleic acid copolymer is added. 17. The method according to any one of the preceding claims, characterized in that the methyl vinyl ether / Maleic anhydride copolymers containing an unsaturated surfactant, a fatty vinylidene or networking agents are used. 909081 / US? BATH 18. Method according to one of the preceding claims, due to the fact that the methyl vinyl ether / Maleic anhydride mixed polymers with an epoxy compound with a content of many -OH-, -SH- or -NH groups linked simultaneously with the hydrolysis of the anhydride groups « 19. Procedure "according to claim 18" characterized by the fact that! "· one as a crosslinking agent Polyethylene glycol used, 20. "" A method according to, einero of the preceding claims, characterized in that one means _p @ wi substituted HydroxybenzoeMßOßiSp ssabstituiert® Hydrossybenzoate, Kthylendiamintetraeesi ^ sa ^ s © $ e-Hydssscyehinolin nnä Fentachlorphenyllaurat to Verbesseraag resistance d © s interpolymers gegeis maybe I * _f Holds _ff © Kydative degradation or biological attack is added to the reaction mixture before or after hydrolysis of the Afshfiridgruppen .. 21 «Veffate © il iiaeh one of the preceding claims, it is known that a proportion of the anhydride groups with an alcohol or an amine at the same time with the hydrolysis of the B @ stest. ' 90 9 881 / 1A 57 ' Μ- 22. The method according to claim 21, characterized in that up to 2ot of the anhydride groups are reacted with an alcohol or an amine at the same time as the hydrolysis of the remainder. 23. Use of a methyl vinyl ether / maleic acid mixed polymer according to one of the preceding claims as a thickener in one approach. 90988 1/1 4 57