JPH0477507A - Compatibilizing agent and polymer blend c0mp0siti0n - Google Patents

Abstract

PURPOSE:To obtain a compatibilizing agent effective for improving impact resistance, mechanical strength, flexing resistance, etc., of a polymer blend composition consisting of a polar polymer and a polymer having poor polarity, comprising a polymer of polymerizable monomer containing an oxazine group, etc. CONSTITUTION:A compatibilizing agent comprising a polymer of a polymerizable monomer containing an oxazine group shown by formula I (R1 to R4 are H or substituent group) or an oxazolone group shown by formula II, etc., in the molecule and improving compatibility of different polymers having poor compatibility.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a compatibilizer for improving the compatibility of different polymers and a polymer blend composition containing the compatibilizer.

(Prior Art) Attempts to obtain polymeric materials with improved strength characteristics, processability, etc. by blending different types of polymers have been widely carried out in the field of polymers. It is well known that in polymer blending, various properties of the resulting polymer material are affected by the compatibility of the blended polymers, and styrene-butadiene is used as a compatibilizer to improve compatibility. Methods using maleated products of brosox copolymer or styrene/butadiene copolymer have been proposed (for example, JP-A-47-11486, JP-A-50-75651, JP-A-56). -100840
Publications, etc.).

(Problems to be Solved by the Invention) These methods are effective when blending different types of polar polymers, but a sufficient compatibilizing effect cannot be obtained when blending non-polar polymers and polar polymers. There is also a need for the development of compatibilizers that improve compatibility in polymer blends.

In view of this background, the present inventors conducted intensive research to develop a new compatibilizing agent and discovered that a polymer having a specific functional group is effective as a compatibilizing agent for a blend of different polymers. Based on this knowledge, we have completed the present invention.

(Means for Solving the Problems) According to the present invention, the compatibility of a heterogeneous polymer with poor compatibility characterized by containing a polymer of a polymerizable monomer having an oxazine group or an oxazolone group can be improved. A polymer blend composition is provided comprising a compatibilizer for improving compatibility, a dissimilar polymer having poor compatibility, and the compatibilizer.

Hereinafter, the configuration of the present invention will be explained in detail.

(Compatibilizer) The dispersant of the present invention which contains oxazine has an oxazine group in the molecule.
→- (in the formula, R1 to R4 represent hydrogen or a substituent), and preferably contains about 0.01 to 10% of the group.

→C-C)1. →- /\ or R2-C-C-0 (in the formula, R1 to R3 represent hydrogen or a substituent) C in the formula RI
"" R3 represents hydrogen or a substituent. ) and preferably contains about 0.01 to 10% of the group.

S6-11 Notice S The compatibilizer having the above structure of the present invention may be obtained by polymerizing the polymerizable monomer having the above-mentioned reactive group in the molecule together with other polymerizable monomers if necessary. I can do it.

Examples of the polymerizable monomer having an oxazine group include 2-vinyl-2-oxazine, 2-vinyl-4-methyl-2-oxazine, 2-vinyl-4-ethyl-2-oxazine,
2-isopropenyl-2-oxazine, 2-isopropenyl-4-methyl-2-oxazine, 2-isopropenyl-4-ethyl-2-oxazine, 2-isopropenyl-4,5dimethyl-2-oxazine, etc. Can be mentioned.

Examples of polymerizable monomers having an oxazolone group include 2-vinyl-5-oxazolone, 2-vinyl-4-methyl-5
-oxazolone, 2-vinyl-4=ethyl-5-oxazolone, 2-impropenyl-5-oxazolone, 2-
Examples include isopropenyl-4-methyl-5-oxazolone, 2-isopropenyl-4-ethyl-5-oxazolone, and 2-isopropenyl-4,4-dimethyl-5-oxazolone. Also, 2-vinylidene-4-methyl-3-
Oxazolin-5-one, 2-vinylidene-4-isopropyl-3-oxazolin-5-one, 2-isopropylidene-4-methyl-3-oxazolin-5-one, 2
-isopropylidene-4-phenyl-3-oxazolin-5-one, 2-isopropylidene-4-t-butyl-
Also included are polymerizable monomers (psudoxazolone) having an oxazolone group in the main chain of the molecule, such as 3-oxazolin-5-one.

Monomers used as necessary with these monomers are not particularly limited as long as they can be copolymerized, such as styrene monomers such as styrene, p-methylstyrene, and p-methoxystyrene; acrylic acid Acrylic acid or methacrylic acid monomers such as , methyl acrylate, butyl acrylate, stearyl acrylate, methacrylic acid, methyl methacrylate; ethylene, propylene, vinyl chloride, vinyl acetate, acrylamide, acrylonitrile, N-vinylpyrrolidone, etc. One or more of these may be used.

In particular, as a polymerization initiator used for polymerization which is preferred because it is easy to copolymerize styrene monomers, commonly used oil-soluble peroxide-based or azo-based initiators can be used.

For example, peroxide initiators such as benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2' Azubis-(2,4-dimethylvaleronitrile), 22'-azobis-2,3,3-trimethylbutyronitrile, 1,1'-azobis-(cyclohexane-
1 carbonitrile), 4,4'-3azobis-4cyanovaleric acid, and dimethyl-2,2'-azobisisobutyrate. The polymerization initiator is
It is preferably used in an amount of 0.05 to 10% by weight based on the polymerizable monomer.

Examples of the polymerization solvent include acetonitrile, nitromethane, toluene, henzene, and xylene, which may be used alone or in combination. Polymerization temperature is usually 20°C
~150°C, preferably 0°C to 120°C.

Furthermore, the polymer used in the present invention can also be produced using a common anionic polymerization catalyst (for example, an organic lithium compound).

The compatibilizer of the present invention thus obtained has at least one heterocycle in the polymer chain, and the content of the heterocycle varies depending on the molecular weight of the polymer, but is usually (weight average Molecular weight)/(-number of heterocycles in molecule) is preferably 200,000 or less, more preferably 1
00,000 or less, more preferably 10,000 or less. However, when it is less than 1,000, the effect as a compatibilizer becomes saturated. Further, the composition of the polymer is not particularly limited in the present invention, and the solubility parameter (SP
) It is desirable to select a polymer having a composition that gives an SP value close to the value.

Even if the polymer components to be blended are different types of polymers with poor compatibility, the compatibilizer of the present invention will not have a compatibility improvement effect if both of the polymer components are non-polar, and if one of the polymer components is polar. When one polymer is less polar than the other, a significant compatibilizing effect can be obtained.

The amount of the compatibilizer to be used is not particularly limited and varies depending on the polymer components to be blended, but it is usually used in an amount of 1 to 800% by weight, preferably 5 to 30% by weight, based on the Friend polymer.

The polymer blend composition of the present invention contains a less compatible heterogeneous polymer component and the compatibilizer of the present invention. The first polymer component is a polar polymer and the second polymer component is a polar polymer.
It is a polymer that is incompatible (not compatible at all or has poor compatibility) with the components.

Examples of the polar polymer as the first component include addition polymers and condensation polymers containing atoms such as oxygen, sulfur, nitrogen, or halogen, and halogen-containing addition polymers. These atoms include carboxyl groups, dithiocarboxyl groups, thiocarboxyl groups and their metal bases, acid anhydride groups, halogenated acyl groups, hydroxyl groups, thiol groups, ester groups, thioester groups, ether groups, thioether groups, amino groups, It exists in polymers as polar groups such as amide groups, imide groups, ammonium bases, isocyanate groups, urethane groups, and sulfonyl halogen groups.

Hydroxyl group-containing polymers include polyvinyl alcohol, polyvinyl butyral, partially saponified ethylene-vinyl acetate copolymers, etc.; ester group-containing polymers include polymethyl methacrylate, acrylics such as copolymers of methyl methacrylate and acrylic esters, etc. resins, polycarbonates obtained by condensation polymerization of bisphenol A and phosgene, polycarbonates obtained by transesterification of bisphenol A and diphenyl carbonate, condensation polymers of aromatic dicarboxylic acids and diols (e.g. polyethylene terephthalate, polybutylene terephthalate, roseoxy) benzoyl polyester, etc.), thermotropic liquid crystal polymers made from aromatic dicarboxylic acids/aromatic diols, etc., polyarylate resins, cyclic lactones (e.g. β-
(propiolactone, ε-caprolactone, etc.), cellulose derivative resins (e.g. cellulose propionate, cellulose acetate, etc.); (thio)ether group-containing polymers include polyphenylene oxide and its modified products, polyphenylene sulfide, Acetal resins (e.g. polyoxymethylene, copolymers of formaldehyde and α-olefin, etc.); examples of amide group-containing polymers include aliphatic polyamides (e.g. nylon 6, nylon 66,
Nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-nylon 66 copolymer, nylon 6-nylon 12 copolymer, etc.; as imide group-containing polymers, polyoxydiphenylenepyromellitimide,
Polyamino bismaleimide, etc.; urethane group-containing polymers include thermoplastic polyurethanes (e.g. B, F, Good
ESTANE manufactured by Rich, PE manufactured by Upjohn
LETHANE, DESMOPAN manufactured by Bayer, etc.); examples of halogen-containing polymers include polyvinyl chloride,
Polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymer, chlorinated polyethylene, chloroprene rubber, epichlorohydrin rubber, fluororubber (e.g. vinylidene fluoride copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene) -perfluoromethyl vinyl ether copolymer, etc.), chlorinated butyl rubber, brominated butyl rubber, etc.; Other polar polymers include chlorosulfonated polyethylene, polyvinyl acetate, ethylene-vinyl acetate copolymer, polysulfone (bisphenol A and dichloro Examples include condensation polymers of diphenylsulfone), polyethersulfones (for example, VICTREX manufactured by IC1), ABS, acrylonitrile-styrene resins, acrylonitrile-butadiene copolymers, and the like. It goes without saying that these polymers should have the necessary molecular weight and melting point for crystalline polymers to satisfy processability, strength, and other required properties. The polymer may be resin-like or rubber-like, and is appropriately selected depending on the intended use of the polymer blend composition.

The second polymer component in the composition of the present invention is the first polymer component described above.
There are no particular restrictions on the polymer as long as it is incompatible with the polymer component. Further, both the first and second polymer components may belong to the above-mentioned first polymer component and may be mutually incompatible polymers. Polymers that are incompatible with the above first polymer component include polystyrene, impact-resistant polystyrene resin, polyethylene, polypropylene, ethylene-propylene copolymer, poly-4-methylpentene-1, polybutene-1, and butyl rubber. , EPDM polybutadiene,
Polyisoprene, styrene-butadiene copolymer (random copolymer; block copolymers such as A-B type and A-B-A type), styrene-isoprene copolymer (random copolymer; A-B type) , AB-A type block copolymers), polyisobutylene, polybutene resins, and the like. It goes without saying that these polymers should have the necessary molecular weight and melting point for crystalline polymers to satisfy processability, strength, and other required properties. Further, the polymer may be resin-like or rubber-like, and is appropriately selected according to the intended use of the polymer blend composition.

In the polymer blend composition of the present invention, the combination of each component polymer is not particularly limited, and the optimum combination that matches the intended use of the composition is selected. Each component polymer may be used alone or in combination of two or more. Furthermore, the blend ratio of each component polymer is not particularly limited, and is determined so as to satisfy the intended use and required performance of the composition. Usually, the first polymer component is 95 to 5% by weight and the second polymer component is 5 to 95% by weight (based on all polymer components).

The polymer blend compositions of the present invention can be prepared using mixing machinery used in conventional polymer blending. Examples of the mixing machine include a mixing roll, a Hanhari mixer, an internal mixer, a kneader, and an extruder.

The compatibilizer of the present invention can be added together when mixing different types of polymers, or after it has been mixed with a polymer component of lower polarity in advance,
It can be used by mixing with a polar polymer, etc.

Moreover, various compounding agents can be added to the polymer blend composition of the present invention within a range that does not impair its properties.

The type and amount of compounding agents to be used are determined depending on the intended use of the composition, and are not particularly limited in the present invention.

(Effects of the Invention) The compatibilizer of the present invention exhibits a remarkable effect on compatibilizing different polymers with poor compatibility compared to conventional compatibilizers such as styrene-butadiene floc copolymer, and particularly It shows a remarkable effect on improving the strength properties such as impact resistance, mechanical strength, and bending resistance of polymer blend compositions consisting of a polar polymer and a less polar polymer.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

Synthesis Example 1 A flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, and a thermometer was charged with 250 parts of toluene in which 3 parts of isopropenyloxazine and 97 parts of styrene were dissolved.

Furthermore, 4110 parts of hengeyl peroxa were added. It was heated to 80 to 100° C. while blowing nitrogen gas, and polymerized in this state for 5 hours while stirring. After the temperature was returned to room temperature and the solvent was removed by evaporation, the mixture was poured into 500 parts of methanol, solidified, and dried to obtain a polymer having an oxazine group as a functional group. This polymer was designated as compatibilizer A.

Synthesis Example 2 In Synthesis Example 1, the polymerizable monomer used was styrene 98
The same method as in Synthesis Example 1 was repeated except that 1 part and 2 parts of isopropenyl oxazolone were used to obtain a polymer having an oxazolone group as a functional group.

This polymer was designated as compatibilizer B.

Synthesis Example 3 In Synthesis Example 1, the polymerizable monomer used was styrene 98
A polymer having an oxazolone ring as a functional group in the main chain was obtained by repeating the same method as Synthesis 1 except that 2 parts and 2 parts of 2-isopropylidene-4-methyl 3-oxazolin-5-one were used. This polymer was designated as compatibilizer C.

Example 1 30% benzene solution of polystyrene (weight average molecular weight 50,000) and polycarbonate (Taflon 2 manufactured by Idemitsu Petrochemical Co., Ltd.)
200 ) of 30% benzene solution for 10 m each! The mixture was placed in a test tube with a sealed stopper (diameter 1.4 cm, length 21 cm), thoroughly shaken by hand, and the state of phase separation was observed depending on the standing time.

The length of the transparent lower phase (polycarbonate) was used as a measure of phase separation. That is, the longer the length of the lower phase, the easier it is to phase separate. The results are shown in Table 4. Note that the amount of the compatibilizer used is the weight fraction relative to the polycarbonate.

Table 1 The results in Table 1 show that the compatibilizing agent of the present invention is effective in compatibilizing polystyrene and polycarbonate.

Example 2 20 parts of polystyrene, 80 parts of the polar polymer listed in Table 2, and a compatibilizer (10% relative to the polar polymer) were melt-kneaded using an extruder to obtain a pelletized blend polymer composition. Ta. This pellet was press-molded to prepare a test piece, and the impact strength and tensile strength were measured. The results are shown in Table 2.

Claims (3)

[Claims] (1) A compatibilizing agent for improving the compatibility of heterogeneous polymers with poor compatibility, characterized by containing a polymer of a polymerizable monomer having an oxazine group or an oxazolone group. (2) The compatibilizing agent according to claim 1, wherein the polymer is a copolymer of the monomer and a monomer copolymerizable with the monomer. (3) A polymer blend composition comprising a heterogeneous polymer having poor compatibility and a compatibilizer according to claim (1) or (2).