JPH0257571B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful method for blending two or more polymers. Specifically, in producing a resin composition that is a blend of two or more polymers having a desired composition, an organic solvent solution containing the polymer that is substantially insoluble in water and an aqueous solution containing a water-soluble polymer dispersant are used. It relates to a method in which polymers can be blended very easily by distilling off an organic solvent and then removing water from a liquid mixture consisting of the following. In the polymer industry, a large number of synthetic polymers have been studied, and a wide range of materials such as molded bodies, films, and fibers have been developed. In recent years, in response to diversifying needs and in pursuit of better properties, the development of materials from single polymers to multicomponent polymers of two or more types has become active. One of the means for realizing such a multi-component material is a method of physical blending, which is outlined in Polymer Alloy (edited by The Society of Polymer Science, 1981), pp. 3-10. According to detailed literature, physical blends include latex blends, solvent cast blends, and melt blends. Latex blending and solution blending are sometimes applied as a pre-operation for melt blending or kneading blending, in which polymers are mixed and dispersed in a dispersion medium beforehand and blended, and polymers are co-produced from the dispersion medium without impairing the dispersion state. It is separated by precipitation, salting out, and used as a kneaded blend sample. In many cases, it is not easy to uniformly mix two or more types of polymers. In order to obtain better properties, it is necessary to achieve a dispersion state as fine as possible, but in the field of plastics, heating rolls, Banbury mixers, single-screw and twin-screw kneaders, extruders, etc. Blended materials have been produced. However, direct blending is difficult when there is a large difference in plasticizing temperature or when the melt viscosity is significantly different.
Preliminary dispersion is required. In the case of heat-resistant polymers, so-called engineering plastics, they inherently have a high plasticity temperature, and conventional methods are subject to restrictions on the resins that can be blended with them. Furthermore, if the Kano kneading is repeated to obtain a more sufficient dispersion state, the polymer will suffer from thermal deterioration due to the high temperature, and the excellent properties of the polymer will be lost. Furthermore, energy loss is also large. Therefore, a simpler and more economical blend of polymers has been desired. The method of the present invention is generally a new and useful method that can be applied to blends of any composition to be subjected to this milling blend. In the present invention, the polymer is used as a solution in an organic solvent that is substantially immiscible with water. Its concentration is 1 to 80% by weight, preferably 5 to 30% by weight. If it is less than 5%, the amount of organic solvent to be distilled off is too large, and if it exceeds 30%, the solution becomes too viscous and cannot be mixed sufficiently with the aqueous layer. As the organic solvent, any organic solvent that is substantially immiscible with water and that dissolves the polymer can be used. Preferably, it serves as a common solvent for two or more types of polymers. In the present invention, water containing a water-soluble polymer dispersant is used. The amount thereof is 50 to 10,000 parts by weight per 100 parts by weight of the above-mentioned heavy solution. The concentration of the dispersant is 0.001 to 1% by weight, preferably 0.005 to 0.5% by weight. Although it is possible to use more than 1% by weight, the organic solvent to be distilled off may foam, which is not preferable in terms of operation. The water-soluble polymer dispersant used in the present invention includes:
All conventionally known materials can be used, but preferably carboxymethyl cellulose, oxyethyl cellulose, styrene-maleic acid copolymer and its derivatives, polyvinyl alcohol and its derivatives,
Polyvinylpyrrolidone, polyvinylpyridine-N
- oxide, polyalkylene oxide and its derivatives, sodium alginate and its derivatives, and lignin sulfonate, or a mixture of two or more thereof. Among these, styrene-maleic acid copolymers and their derivatives, polyvinyl alcohol and its derivatives, and polyvinylpyrrolidone are more preferred in that they do not produce particles with large diameters. Particularly preferred is polyvinyl alcohol, which has a degree of saponification of 60 to 100 mol% and a viscosity of a 4% aqueous solution (at 20°C) of 15 to 100 cps. Furthermore, by using polyalkylene oxide in an amount of 0.001 to 1% by weight based on water, foaming during solvent distillation is completely eliminated, and the process becomes stable.
It has the advantage that the solvent distillation time can be significantly shortened. The molecular weight of the above water-soluble polymer dispersants is 5000~
1000000 is preferred. The two liquids may be mixed by simply vigorous stirring, or by circulation using an ultrasonic mixer or a pump. Next, the organic solvent is distilled off from the dispersed mixture by heating and/or under reduced pressure, either continuously or in batches. At this time, water or hot water may be added during distillation if necessary. Polymers that can be used in the present invention include aromatic or aliphatic polyesters, polycarbonates, polyester carbonates, polyamides, polyamide esters, polysulfonates, polyphosphonates,
These include polyester ether, polyallyl sulfone, polyarylene sulfide, polyarylene oxide, polyacetal, and polyvinyl polymer. Aromatic or aliphatic polyesters have the general formula It is expressed as Polycarbonate has the general formula It is expressed as Polyester carbonate has the general formula or It is expressed as In addition, polyamide has the general formula It is expressed as Polyamide ester has the general formula or It is expressed as Polyester has the general formula

[Formula] or

Represented by [Formula]. Polysulfonate is represented by the general formula -(O- _SO2 -A- _SO2 -O-B-). Polysulfonate is represented by the general formula -(O- _PO2 -A- _PO2 -O-B-). Polyaryl sulfone is represented by the general formula -(Ar-SO ₂ -). Polyarylene sulfide is represented by the general formula -(Ar-S-). Polyarylene oxide is represented by the general formula -(Ar-O-). Polyacetal has the general formula It is expressed as Polyvinyl polymer has the general formula It is expressed as In the above general formula, A to D are aromatic and aliphatic divalent residues, Ar is a divalent aromatic residue, and R ₁
~R ₄ represents a monovalent aliphatic, aromatic, or halogen atom. Among these polymers, it can be applied to all those that are soluble in organic solvents that are substantially immiscible with water. In particular, when one of the polymers is an aromatic polyester, an aromatic polycarbonate, or an aromatic polyester carbonate, the industrial production method is such that the polymer is obtained as a solution in a water-immiscible organic solvent such as methylene chloride; Since other resins can be dissolved in the solution and blended by the method of the present invention,
It is very advantageous as an industrial process. More preferably, the polymer is an aromatic polyester copolymer, and specifically, the aromatic polyester copolymer has the general formula (Ar, Ar': divalent aromatic group). More specifically, Ar,
Ar′ is represented by the following general formula. [In the formula, n: an integer of 0 to 2, p, q: an integer of 0 to 4, R ₁ , R ₂ ; an alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, an alkoxyl group, an allyloxyl group, and an allyl group. Alkoxyl group and its substituted product or halogen atom, X; covalent bond, carbon number 1-10
represents an alkylene group, a cycloalkylene group or cycloalkylidene group having 5 to 15 carbon atoms, and derivatives thereof, -O-, -S-, -CO-, _-SO2- (provided that the substituents on each benzene nucleus may be different from each other, and may also be different in type and position for each benzene nucleus). ]Specifically, aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether dicarboxylic acid, 4-
4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, etc., and bisphenol components include bis(4-hydroxyphenyl). ) methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-
3,5-dimethylphenyl)methane, bis(4-
hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, bis(4-hydroxy-3,5
-difluorophenyl)methane, bis(4-hydroxy-3,5-diphenylphenyl)methane,
Bis(4-hydroxyphenyl)-ketone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl sulfone), 4,4'-dihydroxydiphenyl ether, 1,1-bis(4-hydroxy phenyl)ethane, 2,2-bis-(4-hydroxyphenyl)propane, 2,
2-bis(4-hydroxy-3-methylphenyl)-propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2
-bis(4-hydroxy-3,5-diphenylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,
2-bis(4-hydroxy-3,5-dichlorophenyl)propane, bis(4-hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4 '-Methylphenylmethane, 1,
1-bis(4-hydroxyphenyl)-2,2,
2-trichloroethane, bis(4-hydroxyphenyl)-(4'-chlorophenyl)methane, 1,1
-Bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)-cyclohexylmethane, 4,4-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, hydroquinone, resorcinol, 2,6-dihydroxy Toluene, 2,6-dihydroxychlorobenzene,
Examples include 2,6-dihydroxytoluene. Aromatic polyesters are produced from these aromatic dicarboxylic acid chlorides and bisphenols, for example, by interfacial polycondensation. At this time, the polymer is obtained as a solution in a halogen solvent such as methylene chloride. A solid or solution of the other types of polymers or other aromatic polyesters described above is added to this solution or a separately prepared solution to create a polymer blend solution with a desired composition, and then a water-soluble polymer dispersion is performed. dispersed in an aqueous solution containing the agent. Of course, the addition of the second polymer or polymer solution can be added to the first
This may be done after dispersing the second solution in water.
In this manner, the organic solvent is gradually distilled off from the aqueous dispersion of the solution containing the produced different polymers while heating and, if necessary, reducing pressure. The fact that the method of the present invention does not cause particles to fuse to each other or adhere to the vessel wall cannot be inferred from conventional knowledge. The blend is then separated from the solution as particles and the water removed using conventional isolation techniques such as decantation, filtration or centrifugation. Furthermore, by passing through a drying step, polymer powder or particles can be obtained. According to the invention, the granules generally have a bulk density of
It has a fairly uniform particle size, ranging from 0.2 to 0.7 g. Further, the water-soluble polymer dispersant used is removed together with water, so that it does not substantially remain in the granules. Therefore, it is also possible to reuse the aqueous solution. Fillers, pigments, stabilizers, mold release agents, and various other materials can be added to the obtained granules according to conventionally known methods. These blends or the granules themselves can be subsequently processed through a chipping process or directly.
Moreover, when a fine powder is obtained, it can also be used for powder coating. Examples are shown below, but the present invention is not limited thereto. Reference example 1 Production of aromatic polyester Bisphenol A 223.7g, 3,3',5,5'-
Tetramethylbisphenol F 125.6g, paramethoxyphenol 7.0g, sodium thiosulfate
2.4 g of 4N-NaOH, 960 ml, and 1,660 ml of water were mixed in three flasks in a nitrogen atmosphere and cooled to 2° C. to prepare an alkaline aqueous solution of bisphenol. Meanwhile, in another 3 ml flask, 274.1 g of terephthalic acid chloride, isophthalic acid chloride
30.4 g was dissolved in 2500 ml of methylene chloride in a nitrogen atmosphere and cooled to 2°C. 8 In a separable flask, 500 ml of water, 500 ml of methylene oxide, and 4.67 ml of benzyltributylammonium chloride as a catalyst.
g was charged under a nitrogen atmosphere and cooled in the same manner. While vigorously stirring the mixture, each of the above two liquids was continuously added using a pump over 800 seconds. 1.5 hours after the addition was completed, 0.84 g of benzoyl chloride was added to the system dissolved in 100 ml of methylene chloride. After 20 minutes, the stirring was stopped and the polymer was separated into a methylene chloride solution containing the polymer and an aqueous solution containing common salt and caustic soda after about 10 minutes. After decanting the aqueous layer, the same amount of water was added and the mixture was neutralized with a small amount of hydrochloric acid while stirring. After decanting the aqueous layer again, it was washed with water and desalted. This operation 5
Repeatedly. A portion of the polymer solution was taken and the polymer was precipitated with acetone. After drying, the intrinsic viscosity was measured to be 0.56 dl/g (in chloroform, 32°C). Example 1 Blend with polycarbonate A portion of the methylene chloride solution of the aromatic polyester of Example 1, 56 ml (polymer concentration 17.8 wt/vol%)
was placed in a 500 ml separable flask and diluted with methylene chloride to a total volume of 200 ml. Then,
10 g of a commercially available polycarbonate resin Panlite (manufactured by Teijin Ltd.) consisting of bisphenol A and phosgene was added and dissolved with stirring. The solution containing the two types of polymers was homogeneous and transparent. Here, polyvinyl alcohol (saponification degree 88 mol%, 4% aqueous solution viscosity 43 cps)
200 ml of water containing 200 ppm was added and the polymer solution was dispersed by mixing and stirring. Then, set the bath temperature to 45
The mixture was heated to 0.degree. C., and methylene chloride was distilled out while water was gradually added. When 170 ml of methylene chloride was distilled out, the pearl particles in the system were no longer fused together. Then, it was filtered, washed with water, and dried. The particle size of the blend was approximately 0.1 to 2 mm, and was completely uniform when observed under a microscope. When the Koka flow of the blend was measured, the five samples showed the same flow value. The results are shown in Table 1. this is,
It shows that two types of polymers were uniformly blended by the method of the present invention.

[Table] Example 2 In the same manner as in Example 2, a commercially available polysulfone resin consisting of bisphenol A and dichlorodiphenyl sulfone, P, was used instead of the polycarbonate resin.
10 g of -1700 (manufactured by UCR) was used. Table 2 shows the measurement results of Koka type flow.

[Table] Example 3 In the same manner as in Example 1, 10 g of commercially available polystyrene resin was used instead of polycarbonate resin. The results are shown in Table 3.

【table】

Claims (1)

[Scope of Claims] 1. A solution containing two or more polymers dissolved in an organic solvent that is substantially immiscible with water (polymer concentration 1 to 1)
80% by weight) and 50 to 10,000 parts by weight of an aqueous solution containing 0.001 to 1% by weight of a water-soluble polymer dispersant are mixed and dispersed, and then the organic solvent is distilled off from the mixture, and then water A polymer blending method characterized by removing. 2 The water-soluble polymer dispersant is carboxymethyl cellulose, oxyethyl cellulose, styrene-maleic acid copolymer and its derivatives, polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, polyvinylpyridine-N-oxide, polyalkylene oxide and its derivatives, sodium alginate. The blending method according to claim 1, wherein the blending method is one or a mixture of two or more selected from the group consisting of lignin sulfonate, derivatives thereof, and lignin sulfonate. 3. Claim 1, wherein the water-soluble polymer dispersant is one or a mixture of two or more selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol and its derivatives, styrene-maleic acid copolymer and its derivatives. Blending method as described. 4. The blending method according to claim 1, wherein the water-soluble polymer dispersant is polyvinyl alcohol. 5 Saponification degree of polyvinyl alcohol is 60 to 100
Mol%, viscosity of 4% aqueous solution (20℃) is 15-100cps
The blending method according to claim 4. 6. The blending method according to any one of claims 3 to 5, in which polyalkylene oxide is used as a water-soluble polymer dispersant in an amount of 0.001 to 1% by weight of the water used. 7. The blending method according to claim 6, wherein the polyalkylene oxide is polyethylene oxide, polypropylene oxide, or a polyethylene oxide-polypropylene oxide copolymer. 8 The polymer is aromatic or aliphatic polyester, polycarbonate, polyester carbonate, polyamide, polyamide ester, polyester ether, polysulfonate, polyphosphonate, polyallyl sulfone, polyarylene sulfide, polyarylene oxide, polyacetal or polyvinyl The blending method according to claim 1, wherein the blending method is a polymer. 9. The blending method according to claim 1, wherein one of the two or more types of polymers is an aromatic polyester, an aromatic polycarbonate, or an aromatic polyester carbonate. 10 The aromatic polyester polymer has the general formula (Ar, Ar': divalent aromatic group) The blending method according to claim 9, wherein the blending method is represented by: (Ar, Ar': divalent aromatic group). 11. The blending method according to claim 10, wherein Ar and Ar' are represented by the following general formula. [In the formula, n: an integer of 0 to 2, p, q: an integer of 0 to 4, R ₁ , R ₂ ; an alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, an alkoxyl group, an allyloxyl group, and an allyl group. Alkoxyl group and its substituted product, or halogen atom, X; covalent bond, carbon number 1
~10 alkylene groups, cycloalkylene groups or cycloalkylidene groups having 5 to 15 carbon atoms, and derivatives thereof, -O-, -S-, -CO-, SO ₂ - (however, the substitution on each benzene nucleus The groups may be different from each other, and may also be different in type and position for each benzene nucleus). ]