JPH0791339B2 - Polymer polyol manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymer polyol synthesized through a saponification of a vinyl ester copolymer of a low molecular weight ethylene-saturated carboxylic acid and an alkylene oxide addition step. Specifically, synthetic resin raw materials such as saturated polyester, unsaturated polyester, polyol components such as polyurethane, synthetic rubber such as SBR, NBR, CR,
Anti-blooming agents for chemicals added to EPDM, antistatic agents for synthetic resins such as polyethylene, polypropylene, non-drip agents, lubricants, processability improvers, or polymer solid electrolytes, surfactants, wax modifiers The present invention relates to a method for producing a polymer polyol useful as a binder for an inorganic substance.

2. Description of the Related Art Saponified products of ethylene-saturated carboxylic acid vinyl ester copolymers and polymer polyols obtained by adding alkylene oxides to the saponified products are known.

For example, as a method for saponifying a vinyl ester copolymer of ethylene-saturated carboxylic acid, a low molecular weight ethylene-vinyl ester copolymer having a molecular weight of 800 to 4000 is treated with xylene as described in JP-B-52-17558. There is a method in which a wax having a glossiness is produced by dissolving it in a solvent and saponifying it by supplying methanol and a catalyst in an autoclave or using a tower reactor.

Further, as a method for obtaining a polymer polyol by adding an alkylene oxide to a saponified product of an ethylene-saturated carboxylic acid vinyl ester copolymer, ethylene / vinyl acetate molar ratio is as described in US Pat. No. 2,434,179.
An alkylene oxide compound such as ethylene oxide is added to a saponified product of 1/25 to 8/1 ethylene-vinyl acetate copolymer.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, the above-mentioned methods are intended to independently produce saponification and alkylene oxide addition, and are ethylene-saturated carboxylic acid vinyl ester copolymers as starting materials. In order to obtain a polymer polyol by saponifying alkoxide and subsequently adding alkylene oxide, not only is it extremely inefficient and disadvantageous in terms of cost, but a large amount of alkali catalyst is required. There was a large amount of residual alkali, which was a disadvantage in applying it to various applications.

For example, a method for saponifying a vinyl ester copolymer of ethylene-saturated carboxylic acid described in JP-B-52-17558 is disclosed as 60 wt% as a solution of an organic solvent such as xylene.
Since the reaction is carried out at the following concentrations, the recovery of the solvent used is a major issue.

It is effective to use an alkali catalyst for both saponification and alkylene oxide addition. However, if one kind of alkali catalyst is used, the reaction rate for either saponification or alkylene oxide addition will be slow, so a large amount of catalyst must be added. Become.

As a result, a large amount of alkali salt remained in the polymer polyol obtained, and it was a very difficult problem to remove it.

In view of such a point, the present invention is a very simple process in saponifying a vinyl ester copolymer of ethylene and a saturated carboxylic acid, and subsequently adding an alkylene oxide, and yet to produce a polymer polyol having a small residual alkali content. Is what you are trying to do.

Method for Solving Problems The present inventors have arrived at the present invention as a result of extensive studies to solve such problems, and flow of a vinyl ester copolymer of ethylene-saturated carboxylic acid by heating and melting. In the resulting polymer polyol, the saponification step and the alkylene oxide addition step are carried out continuously while being treated as an ionic liquid, and the process is simplified and the total amount of catalyst used is reduced by using different alkali catalysts in the saponification step and the alkylene oxide addition step. It serves to reduce the amount of remaining alkali.

That is, the present invention has a two-phase composition of a heat-melted liquid of an ethylene-saturated carboxylic acid vinyl ester copolymer having a number average molecular weight of 800 to 5000 and a saturated carboxylic acid vinyl ester content of 1 to 50% by weight and an aliphatic alcohol. The heterogeneous mixture is partially or completely saponified while removing an alkyl ester of a saturated carboxylic acid, which is a by-product in the presence of an alkali catalyst, outside the reaction system, and then the remaining aliphatic alcohol is removed outside the reaction system. , A method for producing a polymer polyol by subsequently adding an alkali catalyst if necessary and then supplying and adding an alkylene oxide, a vinyl ester of a saturated carboxylic acid is vinyl acetate, and an aliphatic alcohol is methyl alcohol. , The alkali catalyst is sodium hydroxide and / or potassium hydroxide catalyst, and Down oxide is ethylene oxide, more ethylene - vinyl acetate copolymer, the number average molecular weight 1,000 to 4,000, a vinyl acetate content of 10 to 40
The present invention relates to a method for producing a polymer polyol having a weight percentage.

The present invention will be specifically described below.

A vinyl ester copolymer of ethylene and a saturated carboxylic acid having a number average molecular weight of 800 to 5000 and a vinyl ester content of a saturated carboxylic acid of 1 to 50% by weight used in the present invention is produced by a known method. -16755, Japanese Patent Publication No. 60-33154, etc., can be easily produced by a solution-based or gas-phase radical polymerization method, among which it is industrially available and the final product. Number average molecular weight of 1000, which shows the characteristics of polymer polyols
An ethylene-vinyl acetate copolymer having a vinyl acetate content of ˜4000 and a vinyl acetate content of 10 to 40% by weight is preferred.

Examples of the aliphatic alcohol used in the present invention include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and the like, but methyl alcohol is particularly preferable from the viewpoint of the saponification reaction rate and the evaporation recovery property after the reaction.

Examples of the alkylene oxide used in the present invention include ethylene oxide and propylene oxide, but ethylene oxide is particularly preferable from the characteristics of the produced polymer polyol.

It is well known that an alkali catalyst is effective in saponifying a vinyl ester copolymer of ethylene and a saturated carboxylic acid and subsequently adding an alkylene oxide, and is typified by an alkali metal hydroxide and an alcoholate. As a result of various studies as the alkali catalyst used in the present invention, sodium hydroxide was used in the saponification step and potassium hydroxide was used in the alkylene oxide addition step, so that the residual amount of alkali in the polymer polyol as the final product was significantly increased. It is particularly preferable because it can be reduced to

The saponification reaction in the present invention may be either a batch system or a continuous system and can be achieved by heating a mixture of a vinyl ester copolymer of ethylene and a saturated carboxylic acid, an aliphatic alcohol and an alkali catalyst.

At this time, an alkyl ester of a saturated carboxylic acid is by-produced with saponification, but if it is not removed from the reaction system, the catalytic efficiency will be poor, and since the alkali catalyst will become a salt and reduce the catalytic effect, evaporation of the aliphatic alcohol It is effective to distill it out of the reaction system together under the conditions.

After completion of the saponification reaction, the temperature is raised to completely distill off the aliphatic alcohol and the alkyl ester of by-product saturated carboxylic acid outside the system, thereby completely removing the aliphatic alcohol that interferes with the subsequent alkylene oxide addition step. can do.

If necessary, an alkali catalyst is additionally added to the thus obtained vinyl ester copolymer of ethylene and a saturated carboxylic acid, and alkylene oxide is supplied at a high temperature to produce a polymer polyol.

The saponification rate of the vinyl ester copolymer of ethylene and saturated carboxylic acid is not particularly limited, but 50 to 100% is preferable in order to obtain the characteristics as the polymer polyol of the final product.

Although the supply amount of alkylene oxide is not particularly limited,
Addition of 20 to 1000 parts by weight to 100 parts by weight of a saponified product of a vinyl ester copolymer of ethylene and a saturated carboxylic acid is preferable to obtain the characteristics as a polymer polyol of the final product.

It is economical to continuously carry out the saponification reaction and the alkylene oxide addition reaction in the same reactor, and once the saponification reaction product is taken out from the container, it is a great waste in terms of workability and efficiency.

The saponification reaction may be carried out by mixing the aliphatic alcohol at atmospheric pressure and around the boiling point for about several hours, and the alkylene oxide addition reaction may be carried out at about 100 to 200 ° C. under several atmospheric pressure for several hours.

In the saponification step of the present invention, the charged amount of the aliphatic alcohol and the alkali catalyst is preferably as small as possible because it is economical and the amount of the residual alkali can be reduced. Therefore, 20 to 1000 parts by weight of aliphatic alcohol, preferably 100 to 500 parts by weight, and 0.01 to 2 parts by weight of alkali catalyst, preferably 0.1 to It is recommended to add 1 part by weight.

As an addition method of the alkali catalyst in the saponification, it can be added all at once or dividedly.

It is preferable that the amount of the alkali catalyst added in the alkylene oxide addition step is as small as possible because it is economical and the amount of the residual alkali can be reduced, but if it is too small, the reaction rate may decrease and the addition may not be sufficiently performed. It is preferable to add it in the range of 0.01 to 2% by weight, preferably 0.1 to 1% by weight, based on 100 parts by weight of the saturated vinyl carboxylic acid copolymer soap. Can be added.

As shown above, the present invention does not use an organic solvent,
Efficiently saponify the molten polymer in the presence of alcohol and alkali catalyst while removing by-products and excess alcohol, and then add an alkali catalyst if necessary without adding it once from the reactor and then add alkylene oxide to achieve extremely high efficiency. It is possible to produce a polymer polyol economically and economically with a small residual alkali amount.

The polymer polyol thus obtained, ethylene-saturated carboxylic acid vinyl ester-at the saponification stage of the copolymer, part or all of the saturated carboxylic acid vinyl ester changes to a vinyl alcohol structure depending on the saponification rate, The completely saponified product has a structure as an ethylene-vinyl alcohol copolymer.

The alkylene oxide adduct as the second step is
It becomes a structure in which alkylene oxide is inserted in the vinyl alcohol part, and shows several to several tens of alkylene oxide chain structures depending on the amount of alkylene oxide added,
Since the molecular terminal has a hydroxyl group, it can be used as a raw material for polycondensation resins, various additives, modification aids, binders and the like.

Examples Hereinafter, examples of the present invention will be specifically shown, and reference examples and application examples will also be shown, but the present invention is not limited thereto.

Reference Example <Production of Ethylene-Vinyl Acetate Copolymer> With a high-pressure reactor, ethylene and vinyl acetate are used in the presence of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator and propane as a molecular weight modifier. Pressure 14
Copolymerized at 00kg / cm ^{2 at} a temperature of 190 ℃ to obtain a vinyl acetate content of 31
An ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) having a weight%, a number average molecular weight of 1800 and a softening point of 30 ° C. was obtained.

Example 1 1 L with a stirrer, a distillation line and a feed line
EVA1 shown in the reference example in the stainless steel autoclave
00 g, 200 g of methyl alcohol and 0.6 g of sodium hydroxide were added, and the mixture was heated and stirred at a temperature of 65 ° C. for 2 hours while the distillation line was opened. After that, the temperature is raised to 14
The temperature was raised to 0 ° C and all the volatile substances were driven out of the system. The saponification product obtained was in the form of a wax with a melting point of 85 ° C, and the saponification rate was 92%.

Subsequently, 0.17 g of potassium hydroxide was added, the temperature was raised to 180 ° C., and then ethylene oxide was added to a pressure of ² kg / cm ² . After confirming the pressure drop due to the addition reaction of ethylene oxide, ethylene oxide was continuously supplied so as to keep the pressure at ² kg / cm ² , and 170 g in total was charged over 1 hour. When the pressure drops to 0.5 kg / cm ² , the temperature is raised to 100 ° C.
As a result of lowering the product to 250 g, a polymer polyol of 250 g was obtained, the melting point of which was 52 ° C., the hydroxyl value was 102 mg KOH / g.
Met.

When the amount of alkali metal was analyzed, sodium 1200
ppm and potassium were 300 ppm.

Example-2 Volume 70 equipped with a stirrer, a distillation line and a feed line
The EV shown in the reference example was placed in a 0 L stainless steel autoclave.
A 160kg, methyl alcohol 320kg and sodium hydroxide 0.9
6 kg was charged, and the mixture was heated and stirred at a temperature of 65 ° C. for 2 hours while the distillation line was opened. After that, the temperature was raised to 142 ° C. over 1 hour to expel all the volatile substances out of the system. The saponification product obtained was in the form of a wax with a melting point of 83 ° C, and the saponification ratio was 90%.

Subsequently, 0.27 kg of potassium hydroxide was added, the temperature was raised to 180 ° C., and then ethylene oxide was added to a pressure of ² kg / cm ² . After confirming the pressure drop due to the addition reaction of ethylene oxide, ethylene oxide was continuously supplied so as to keep the pressure of ² kg / cm ² , and a total of 272 kg was charged over 1 hour. When the pressure drops to 0.4 kg / cm ² , raise the temperature to 100
As a result of lowering the temperature to ℃ and taking out the product, 408 kg of polymer polyol was obtained, its melting point was 51 ℃, hydroxyl value was 110 mgK
It was OH / g.

When the amount of alkali metal was analyzed, sodium 1200
ppm and potassium were 300 ppm.

Example-3 In a 1 L autoclave shown in Example 1, 100 g of EVA shown in Reference Example, 100 g of methyl alcohol and sodium hydroxide were added.
Add 0.3g and add sodium hydroxide from the feed line.
While supplying 100 g of methyl alcohol in which 3 g was dissolved over 2 hours, the distillation line was opened and the mixture was heated and stirred at a temperature of 65 ° C. for 2 hours. After that, the temperature was raised to 140 ° C over 1 hour to expel all the volatiles out of the system to obtain a saponified product having a melting point of 87 ° C. The saponification rate was 94%.

Subsequently, 0.17 g of potassium hydroxide was added, the temperature was raised to 180 ° C., and then ethylene oxide was added to a pressure of ² kg / cm ² . After confirming the pressure drop due to the addition reaction of ethylene oxide, ethylene oxide was continuously supplied so as to keep the pressure at ² kg / cm ² , and 170 g in total was charged over 1 hour. When the pressure drops to 0.5 kg / cm ² , the temperature is raised to 100 ° C.
As a result of lowering the product to 251 g, a polymer polyol of 251 g was obtained, which has a melting point of 50 ° C. and a hydroxyl value of 105 mg KOH / g.
Met.

When the amount of alkali metal was analyzed, sodium 1200
ppm and potassium were 300 ppm.

Example-4 100 kg of EVA, 320 kg of methyl alcohol and 1.96 kg of sodium hydroxide shown in the reference example were put into the 700 L autoclave shown in Example 2 and reacted in the same manner as in Example 2.

The obtained saponified product had a melting point of 80 ° C. and was waxy, and the saponification rate was 88%.

Then, ethylene oxide was intermittently supplied at a pressure of ² kg / cm ^{2 in} the same manner as in Example 2 without adding an alkali, and a total of 170 kg was charged over 2 hours to carry out a reaction to obtain 253 kg of a polymer polyol having a melting point of Is 38 ℃, hydroxyl value is 102mgKOH / g
Met. Moreover, when the amount of potassium was analyzed, it was 4000 ppm.
Met.

Despite the use of a large amount of potassium hydroxide, no particularly high reactivity was exhibited, it took a long time to add ethylene oxide, and the amount of residual potassium increased.

Example-5 In the same manner as in Example 1, 100 g of EVA shown in Reference Example, 200 g of methyl alcohol and 0.6 g of sodium hydroxide were put into a 1 L autoclave to obtain a saponified product having a melting point of 85 ° C and a saponification rate of 92%. .

Subsequently, ethylene oxide was added at 180 ° C. to carry out an addition reaction, but only 48 g of ethylene oxide could be introduced even after 3 hours.

Example-6 In the same manner as in Example 1, 100 g of EVA shown in Reference Example, 200 g of methyl alcohol and 0.6 g of sodium hydroxide were put into a 1 L autoclave to obtain a saponified product having a melting point of 85 ° C and a saponification rate of 92%. .

Subsequently, 0.3 g of sodium hydroxide was added, and ethylene oxide was added to carry out an addition reaction, but only 3 g of ethylene oxide could be introduced even after 3 hours.

As a result of taking out the product, 143 g of a polymer polyol was obtained and contained 3500 ppm of sodium.

Application example <Antistatic property of polyethylene sheet> To 100 parts by weight of ethylene-vinyl acetate copolymer resin (Evatate H2020 manufactured by Sumitomo Chemical Co., Ltd.), 2 parts by weight of the polymer polyol produced in Example 2 was added, and the mixture was kneaded and heat-pressed to give a thick film. It
It was a 0.5 mm sheet. Similar sheets were also obtained without addition of polymer polyol.

The surface resistivity of this sheet was measured with a high resistance measuring device after storage at a temperature of 23 ° C and humidity of 50% for 30 hours. As a result, the polymer polyol-free sheet was 10 ¹⁶ ohms or more, while the addition sheet was 10 ¹² It was ohmic and the antistatic effect was recognized.

<Rubber anti-blooming property> 100 parts by weight of ethylene-propylene-diene rubber (Supreme 524 manufactured by Sumitomo Chemical Co., Ltd.), carbon black, process oil, zinc oxide, stearic acid, and a lubricant are added to 100 and 30, respectively.
5, 1 and 3 parts by weight were added and kneaded, followed by 2, 0.5, 0.5 and 1.0 parts by weight of vulcanization accelerators Succinol BZ, TT, TRA and DM, respectively, and 2 parts by weight of the polymer polyol prepared in Example 2. And 1 part by weight of sulfur were added and vulcanized by a conventional method to obtain a sheet having a thickness of 2 mm. Similar sheets were also obtained without addition of polymer polyol.

After leaving these sheets with almost the same glossiness at room temperature for one week, the surface glossiness was observed. I was keeping.

Effects of the Invention As shown above, the present invention has a number average molecular weight of 800 to 5000,
A two-phase heterogeneous mixture of a hot melt liquid of an ethylene-saturated carboxylic acid vinyl ester copolymer and an aliphatic alcohol having a vinyl ester content of a saturated carboxylic acid of 1 to 50% by weight in the presence of an alkali catalyst. After partially or completely saponifying the by-produced alkyl ester of saturated carboxylic acid outside the reaction system, the remaining aliphatic alcohol is removed outside the reaction system, and then an alkali catalyst is additionally added if necessary. It is a method for producing a polymer polyol by supplying and adding alkylene oxide after that. The saponification step and the alkylene oxide addition step are continuously performed, and the saponification step is performed in a two-phase heterogeneous system of a heated molten liquid and an aliphatic alcohol. And saponification step while removing alkyl ester of saturated carboxylic acid generated as a by-product outside the reaction system. Synthetic resin raw material, bloom inhibitor, antistatic agent, anti-drip agent, lubricant, processability improver, by obtaining a polymer polyol with a small amount of residual alkali while optimizing the alkali catalyst in the alkylene oxide addition step to increase the reactivity, It is applied as a polymer solid electrolyte, a surfactant, a wax modifier, an inorganic binder, etc., and its industrial value is high.

Claims (6)

[Claims] 1. A heated molten liquid of a vinyl ester copolymer of ethylene and a saturated carboxylic acid, which has a number average molecular weight of 800 to 5,000 and a vinyl ester content of a saturated carboxylic acid of 1 to 50% by weight, and an aliphatic alcohol. In the presence of an alkali catalyst, the heterogeneous phase mixture is partially or completely saponified while removing the by-produced saturated carboxylic acid alkyl ester out of the reaction system, and then the temperature is raised to remove the residual aliphatic alcohol. And a method for producing a polymer polyol by removing an alkyl ester of a saturated carboxylic acid generated as a by-product outside the reaction system, and subsequently adding an alkali catalyst if necessary, and then adding and adding an alkylene oxide. 2. The method for producing a polymer polyol according to claim 1, wherein the vinyl ester of a saturated carboxylic acid is vinyl acetate. 3. The method for producing a polymer polyol according to claim 1, wherein the aliphatic alcohol is methyl alcohol. 4. The alkali catalyst is sodium hydroxide and / or
Alternatively, the method for producing the polymer polyol according to claim 1, which is potassium hydroxide. 5. The method for producing a polymer polyol according to claim 1, wherein the alkylene oxide is ethylene oxide or propylene oxide. 6. The method for producing a polymer polyol according to claim 2, wherein the ethylene-vinyl acetate copolymer has a number average molecular weight of 1,000 to 4,000 and a vinyl acetate content of 10 to 40% by weight.