JPH02199128A - Modifier for resin - Google Patents

Abstract

PURPOSE:To obtain a modifier which can improve the compatibility of resins without detriment to the flow by using a polymer having a block of a polymer having an affinity for polyamide and a specified block of an aromatic vinyl polymer or the like as a component. CONSTITUTION:A modifier for resin comprising a block of a polymer having an affinity for polyamide and blocks of an aromatic vinyl polymer and/or a polymer having an affinity for polyester. Examples of the process for producing said modifier include one comprising reacting a polymer having a terminal amino and affinity for polyamide with a polymer having a terminal carboxyl and an affinity for aromatic vinyl polymer and/or polyester, and one comprising reacting a polymer having a terminal carboxyl and an affinity for polyamide with a having a terminal group reactive with a carboxyl and an affinity for aromatic vinyl monomer and/or polyester.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a modifier for resins [Prior Art] Modification of resins has been actively studied using polymer blends that blend polymers with different properties. has been done. For example, polymer blends of polyamide resins, polyester resins, and copolymers of ethylenically unsaturated glycidyl compounds are known (for example, JP-A-60-2172
Publication No. 6).

[Problems to be Solved by the Invention] However, the conventional products had problems such as decreased fluidity.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of studies to solve the above problems.

That is, the present invention uses a polymer (a) that has an affinity for polyamide.
) and a block (B) of an aromatic vinyl polymer (b) and/or a polymer (c) having an affinity for polyester.

Polymers (a) that have affinity for polyamides include ring-opened (co)polymers of lactams with three or more membered rings, copolycondensates of amino acids that can be polycondensed, and (co)polymers of dicarboxylic acids and diamines. Examples include polyamides such as condensates, and vinyl polymers containing a vinyl monomer containing a group having affinity for polyamides in the molecule as a constitutional unit.

Ring-opened (co)polymers of lactams with three or more membered rings include ε
- Ring-opened (co)polymers such as caprolactam, dodecanelactam, capryllactam, and enantholactam, and (co)polycondensates of amino acids that can be polycondensed, such as (co)polymers of amino acids such as aminocaproic acid and 11-aminoundecanoic acid. Examples include polycondensates. Dicarboxylic acid and diamine (co)
Polycondensates include diamines such as hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, terminal aminated products of polytetramethylene glycol, and terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. With dicarboxylic acids such as aromatic dicarboxylic acids such as adipic acid, sebacic acid, dodecane di@base acid, aliphatic dicarboxylic acids having 2 to 30 carbon atoms such as geltaric acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Examples include (co)polycondensates and the like.

In a vinyl polymer containing a vinyl monomer as a constitutional unit containing a group having an affinity for polyamide in its molecule, examples of the group having an affinity for polyamide include an epoxy group, an amide group, an imide group, an amino group, and a carholyl group. Examples include acid groups, acid anhydride groups, and hydroxyl groups. Preferred among these are imide groups and acid anhydride groups.

Examples of vinyl monomers having these groups in the molecule include the following unsaturated compounds.

Examples of unsaturated compounds containing epoxy groups include unsaturated glycidyl esters (glycidyl (meth)acrylate, itaconic acid glycidyl esters, butene carboxylic acid esters, etc.), unsaturated glycidyl ethers (allyl glycidyl ether, 2-methylallyl glycidyl ether, etc.), p-glycidyl styrenes (styrene-p-glycidyl ether, etc.), epoxyalkenes (3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy- 1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, etc.) cycloaliphatic epoxy group-containing vinyl compounds (vinylcyclohexene monoxide, etc.).

Among these, preferred is glycidyl methacrylate.

Examples of the amide group-containing unsaturated compound include (meth)acrylamide and the like.

Examples of imide group-containing unsaturated compounds include N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-
Examples include N-phenylmaleimides such as ethyl phenylmaleimide, and alkylmaleimides having 2 to 18 carbon atoms such as N-laurylmaleimide and N-stearylmaleimide. Among these, preferred is N-phenylmaleimide.

As an unsaturated compound containing an amino group, - formula: (in the formula
R4 is hydrogen, methyl group, or ethyl group; R2 is hydrogen,
At least one of the amino groups or substituted amino groups shown in C1-18 alkyl groups, C2-18 alkanoyl groups, phenyl groups, alkyl phenyl groups, and C6-12 cycloalkyl groups). Examples include vinyl monomers contained therein.

Specifically, aminoalkyl esters of (meth)acrylic acid (aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate) etc)
, allylamines ((meth)allylamine, N-methylamine, etc.), vinylamines (N-vinyldiethylamine, N-acetylvinylamine, etc.), aminostyrenes (P-aminostyrene, etc.), and the like.

Among these, dimethylaminoethyl methacrylate is preferred.

Examples of the unsaturated compound containing a carboxylic acid group include (meth)acrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. Among these, maleic acid is preferred.

Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride, chloroitaconic anhydride, chloromaleic anhydride, citraconic anhydride, and the like. Preferred is maleic anhydride.

Examples of hydroxyl group-containing unsaturated compounds include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)
Acrylate, glycerol (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, caprolactone modified 2-
Hydroxyethyl (meth)acrylate, etc., and preferred are glycerol (meth)acrylate and hydroxyethyl methacrylate.

Among the above-mentioned polymers having affinity for polyamides, preferred are polycondensates of diamines and dicarboxylic acids.

As the aromatic vinyl polymer (b), an aromatic vinyl compound or a polymer or copolymer with another vinyl compound copolymerizable with the aromatic vinyl compound can be used.

Examples of this aromatic vinyl compound include styrene, α
-Methylstyrene, dimethylstyrene, t-butylstyrene, vinyltoluene, chlorvinyltoluene, acetoxystyrene, hydroxystyrene, and the like. Other copolymerizable vinyl compounds include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylonitrile, and the like. Among the aromatic vinyl polymers (b), preferred are styrene polymers and styrene/acrylonitrile copolymers.

The number average molecular weight of these aromatic vinyl polymers is usually 1000 to 60000, preferably 3000 to 3000.
It is 0.

Examples of the polymer (c) having affinity for polyester include polycondensates of dicarboxylic acid components such as dicarboxylic acids and/or esters thereof, and diol components.

As the dicarboxylic acid component, the dicarboxylic acids and/or their esters described above in the section of polymer (a) having affinity for polyamide, and two or more thereof are used. Preferred among these are terephthalic acid, isophthalic acid, adipic acid and esters thereof.

Diol components include ethylene glycol, aliphatic diols such as 1゜3-propanediol, 1,4-butanediol, and 1゜6-hexanediol, alicyclic diols such as cyclahexanediol, bisphenol A,
Polyalkylene glycols such as ethylene oxide and/or propylene oxide adducts of bisphenol A, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol, and two or more thereof are used. Preferred among these are ethylene glycol, 1,6-hexanediol and bisphenol A adducts with ethylene oxide and/or propylene oxide.

Further, as well as polycaprolactone and vinyl polymers, (meth)acrylic acid ester polymers are also mentioned as polymers (d) having an affinity for polyesters.

There is no particular restriction on the molecular weight of these polymers, but the number average is usually 1,000 to 50,000, preferably 3,000 to 20
It is 000.

Examples of the method for producing the modifier of the present invention include the following.

(2) A method in which a polymer having an affinity for polyamide having a terminal amino group is reacted with an aromatic vinyl polymer and/or a polymer having an affinity for polyester having a terminal carboxylic acid group, or a method for reacting a polymer having an affinity for a polyamide having a terminal carboxylic acid group, or A method of reacting a polymer having an affinity for a polyamide having an acid group with an aromatic vinyl polymer and/or a polymer having an affinity for a polyester and having an end group reactive with a carboxylic acid group.

(2) A method in which a polymer having an affinity for polyamide having a terminal amino group is reacted with a polymer having an affinity for an aromatic vinyl polymer and/or a polyester having a terminal dicarboxylic acid group.

(2) A method in which an aromatic vinyl polymer having a terminal dicarboxylic acid group and/or a polymer having an affinity for polyester is reacted with a diamine and a dicarboxylic acid.

(2) Method of reacting a vinyl monomer with a polymer having affinity for radiation-treated polyamide Among these methods, methods I and (2) are preferred.

Polymer (a) is a polymer having a terminal amino group in
Examples include various polycondensates and polymers explained in the section. In the case of a polycondensate (co)polycondensate of dicarboxylic acid and diamine, it can be made into a terminal amino group type by changing the reaction molar ratio of dicarboxylic acid and diamine. That is, a terminal amino group type polyamide can be obtained by polycondensing diamine using a molar excess of dicarboxylic acid. Ring-opened (co)polymers of lactams having three or more members and copolycondensates of amino acids capable of polycondensation usually have an amino group at the end.

A vinyl polymer having a terminal carboxylic acid group and having an affinity for aromatic vinyl polymers and/or polyesters is obtained by polymerizing a vinyl monomer in the presence of a chain transfer agent having a carboxylic acid group. can be used. A mercaptan compound can be used as the chain transfer agent. In this case, thioglycolic acid etc. can be used. In the case of a polycondensate having an affinity for polyester, it can be made into a terminal carboxylic acid group type by adjusting the reaction molar ratio of the dicarboxylic acid component and the diol component. That is, by polycondensing the dicarboxylic acid component using a molar excess of the diol component, a polymer having an affinity for a terminal carboxylic acid group type polyester can be obtained.

In the case of a (co)polycondensate of dicarboxylic acid and diamine, which is a polymer with affinity for polyamide having a terminal carboxylic acid group, the product obtained by polycondensation using an excess molar amount of the dicarboxylic acid component than the diol component is used. Can be used. Polycondensates of amino acids that can be polycondensed usually have a carboxylic acid group at one end.

A polymer having an affinity for aromatic vinyl polymers and/or polyesters, which has a group reactive with a carboxylic acid group at the end, and examples of the group reactive with a carboxylic acid group include an amino group,
Examples include hydroxyl group. An aromatic vinyl polymer having a group reactive with a carboxylic acid group at the end and/or a polymer having affinity for polyester, and for vinyl polymers, a chain transfer agent having a group corresponding to the end group. A vinyl monomer polymerized in the presence of can be used.

A mercaptan compound can be used as the chain transfer agent. In the case of a terminal hydroxyl group type, 2-mercaptoethanol etc. can be used, and in the case of a terminal amino group type, 2-aminoethanethiol etc. can be used. As the polymerization method, the same method as in I above is used. In the case of a polycondensation product of a dicarboxylic acid component and a diol component, which is a polymer that has an affinity for polyester, the diol component is polycondensed using a molar excess of the dicarboxylic acid component to create a polymer that has an affinity for terminal hydroxyl group type polyesters. can be obtained.

A method of reacting a polymer having an affinity for polyamide having a terminal amino group with an aromatic vinyl polymer and/or a polymer having an affinity for a polyester having a terminal carboxylic acid group, or a terminal carboxylic acid group An aromatic vinyl polymer having an end group reactive with a carboxylic acid group and/or
Alternatively, as a method for reacting a polymer having affinity with polyester, these polymers may be subjected to a dehydration condensation reaction according to a conventional amide production method or ester production method. At this time, the reaction may be carried out without a solvent or may be carried out using a solvent such as benzene, toluene, xylene, or chlorobenzene.

Furthermore, in order to increase the reactivity, the condensation reaction may be carried out by converting the carboxylic acid group into an acid chloride. Furthermore, a catalyst can also be used. As a catalyst, M g s P t
, S, Ca, Ti, V, Cr, Mn, Fe, Co, Ni
, Cu, Zn, Sr, Mo, Pd.

Su, Ba, and Pb based compounds may be used.

- Examples include amide type condensation reaction, ester type condensation reaction,
A polymer having block (A) and block (B) can be obtained by heating the mixture at 120 DEG C. to 240 DEG C. to carry out a condensation reaction for several hours, and then raising the temperature under reduced pressure.

As the polymer having affinity for the polyamide having terminal amino groups used in (2), the same polymers as in (2) can be used. Examples of polymers having an affinity for aromatic vinyl polymers and/or polyesters having terminal dicarboxylic acid groups include vinyl polymers, which are obtained by polymerizing vinyl monomers in the presence of a chain transfer agent having dicarboxylic acid groups. can be used. As this chain transfer agent, a mercaptan compound can be used. Examples include thiomalic acid. The same polymerization method as in I is used.

The reaction between the above-mentioned polymer having an affinity for polyamide having a terminal amino group and the polymer having an affinity for an aromatic vinyl polymer and/or a polyester having a terminal dicarboxylic acid group is performed by dehydration in the same manner as in I. A condensation reaction may be performed. At this time, a polymer with affinity for polyamide (
The diamines and dicarboxylic acids mentioned under section a) may also be used.

As the polymer having a terminal dicarboxylic acid group and having affinity for aromatic vinyl polymers and/or polyesters in (2), the same polymers as in (2) can be used. As the diamine and dicarboxylic acid, those listed in (2) can be used. The reaction may be carried out in the same manner as in (2) in the presence of a solvent to carry out a dehydration condensation reaction.

In methods (1) and (2) above, a grafted product is obtained in which branches of an aromatic vinyl polymer and/or a polymer having an affinity for polyester are grafted onto the main chain of a polymer having an affinity for polyamide.

As the method (2), various known methods can be used. For example, Polymer Engineering Course 15 Radiation Polymer Chemistry (edited by the Society of Polymer Science and Technology)
p107-136, Special Publication No. 35-7834, Special Publication No. 3
No. 6-3393, No. 36-4250, No. 36-369
Methods such as those described in reference documents such as No. 7 publications can be used.

The modifier of the present invention can be used for various known resins. For example, thermosetting resins (formaldehyde resins, phenolic resins, amino resins, unsaturated polyesters, epoxy resins, diallyl phthalate resins, silicone resins, thermosetting polyurethanes, etc.), thermoplastic resins such as the following, such as polyolefin resins (polyethylene, Polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, poly-4-methylpentene, polybutene, etc.), styrene resin (polystyrene, AS resin, A
BS resin, AAS resin, ABS resin, AC8 resin, MB
S resin, styrene-butadiene resin, HIPS, etc.), polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl butyrate copolymer, ionomer,
Polyacetal, polyamide (nylon 6, nylon 6
6. Nylon 610. Nylon 11. Nylon 12 grade)
, polycarbonate, aromatic polyethers such as polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyether sulfone, polyimide, polyamideimide, polyphenylene sulfide, elastomers (
Ethylene-propylene rubber, ethylene-acrylic ester copolymer, EPDM, butadiene rubber, styrene
It can be used as a modifier for resins such as (hydrogenated) conjugated diene elastomers, polyester elastomers, polyamide elastomers, thermoplastic polyurethanes, etc.) and resin compositions of two or more of these.

Among these, it is preferable to use the resin or resin composition selected from the group consisting of styrene resin, polyamide, polycarbonate, aromatic polyethers, polyethylene terephthalate, polybutylene terephthalate, and polyamide, aromatic polyether, It is particularly preferable to use the resin or resin composition selected from the group consisting of polyethylene terephthalate and polybutylene terephthalate.

The amount of the modifier added to the resin is usually 0.1 to 30 parts by weight per 100 parts by weight of the target resin or resin composition.
Preferably it is 1 to 15 parts by weight.

The present modifier can be mixed with the resin using various known mixers. Examples include an extruder, Brabender, kneader, Banbury mixer, and the like.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. In the following description, parts and %
means parts by weight and % by weight, respectively.

The characteristics of the molded products described in Examples and Comparative Examples were evaluated by the following method.

(1) Impact strength: ASTM D256 notched,
3.2 mm thickness (2) Heat distortion temperature: ASTM D648 (3) Fluidity: The flow length when injection molding was performed using a spiral mold, the so-called spiral flow length (two plate thickness) was measured.

(4) Dimensional change: The difference between the dimensions of the molded product when it is left at 50% humidity and 23°C for 7 days after molding and the dimension of the molded product immediately after molding, expressed as a percentage of the dimensions of the finished product immediately after molding. expressed.

Production Example 1 Hexamethylene diamine 570 parts, adipic acid 34
2 parts of terephthalic acid and 408 parts of terephthalic acid were charged into a stainless steel separable colben, and heated at 180 to 230°C under a nitrogen stream.
Time dehydration polycondensation was carried out to obtain an amino group-terminated polyamide (hereinafter abbreviated as PA-1) having an amine value of 40.

The molecular weight was 2,800. Production Example 2 A flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer, and a gas inlet was charged with 20 parts of styrene, 80 parts of xylene, and 0.1 part of thioglycolic acid. One dropping funnel (dropping funnel 1) was charged with 80 parts of styrene and 0.15 parts of thioglycolic acid. Add 1.2 liters of azobiscyanovaleric acid to the other dropping funnel (dropping funnel 2).
and 20 parts of tetrahydrofuran. The temperature of the liquid in the flask was raised to 80°C, and under a nitrogen stream, the contents were dropped over 3 hours from dropping funnel 1 and over 4 hours from dropping funnel 2 while maintaining the liquid temperature at 80°C. . After the dropwise addition was completed, the temperature was maintained at 80°C for another 2 hours. The polymerization rate of styrene at this time was 98.7%. The solvent was distilled off to obtain 99 parts of polystyrene having terminal carboxylic acid groups (hereinafter abbreviated as PS-1). The molecular weight was 4000 and the acid value was 19.

Production Example 3 Polystyrene having a dicarboxylic acid group at the terminal (hereinafter abbreviated as PS-2) was obtained in the same manner as Production Example 3 except that thiomalic acid was used instead of thioglycolic acid. The polymerization rate of styrene was 97.4%, the molecular weight was 4800, and the acid value was 23.

Production Example 4 200 parts of terephthalic acid and 350 parts of a 2 mole adduct of bisphenol A with propylene oxide were reacted at 140 to 240°C under a nitrogen stream for 8 hours, and then further reacted for 23 hours under reduced pressure.
The reaction was further carried out at 0° C. for 4 hours to obtain a polyester having an acid value of 35 (hereinafter abbreviated as PE5-1).

Example I After reacting 1280 parts of PA-1 and 1295 parts of PS-1 in xylene while dehydrating them for 6 hours, the xylene was distilled off and a modifier of the present invention having an acid value of 1 and an amine value of 10 (hereinafter referred to as 5A-1) was prepared. (abbreviation) was obtained.

Example 2 1560 parts of PA-1 and 490 parts of PS-2 were reacted in the same manner as in Example 1 to obtain a modifier of the present invention (hereinafter abbreviated as 5A-2) having an acid value of 1 and an amine value of 11.

Example 3 After reacting 8 hours while dehydrating 280 parts of PA-1 and 640 parts of PE5-1 in xylene, the xylene was distilled off to obtain a modifier of the present invention having a molecular weight of 8,000 and an amine value of 13 (hereinafter referred to as EA-1). ) was obtained. No acid value was detected.

Example 4 60 parts of nylon 66 (trade name, Leona 66 1300S, manufactured by Asahi Kasei ■, hereinafter abbreviated as PA), 40 parts of modified polyphenylene ether (trade name: Noryl 731J, manufactured by Engineering Plastics ■, hereinafter abbreviated as modified PPE), 5A-15 After blending the parts using a twin-screw extruder at a cylinder temperature of 280℃, the cylinder temperature was 280℃.
The characteristics of test pieces obtained by injection molding at an injection pressure of 800 kg/cm 2 and a mold temperature of 80° C. were evaluated. Further, the molded plate was fractured in liquid nitrogen, and the fractured surface was observed with an electron microscope to measure the dispersed particle size. The results are shown in Table 1.

Example 5 The same operation as in Example 4 was performed except that 5A-2 was used instead of SA-1. The results are shown in Table 1.

Comparative Example 1 The same operation as in Example 4 was performed except that 5A-1 was not used. The results are shown in Table 1.

Example 6 100 parts of PA and 12 parts of EA were blended using a twin-screw extruder in the same manner as in Example 4, and then injection molded and the properties were evaluated. The results are shown in Table 2.

Comparative Example 2 The same operation as in Example 6 was performed except that EA-1 was not used. The results are shown in Table 2.

Example 7 70 parts of PA, polybutylene terephthalate (trade name 1
Made in 401XO6 bundle (hereinafter abbreviated as PBT) 30 copies, E
After blending 15 parts of A-1 using a twin-screw extruder in the same manner as in Example 4, injection molding was performed and the properties were evaluated. The results are shown in Table 3.

Comparative Example 3 The same operation as in Example 7 was performed except that EA-1 was not used. The results are shown in Table 3.

Table 1 Table 2 Table 3 “The effect of invention” The present invention has the following effects.

1. When modifying resin with polymer blend,
It is necessary to increase the compatibility between the resins by some method, but increasing the compatibility often results in a decrease in fluidity, which is a problem when molded products are produced. The modifier of the present invention has the effect of increasing the compatibility between resins without reducing fluidity.

2. By selecting various compositions and structures of the blocks (A) and (B), various polyamide blocks and grafts can be easily obtained.

The modifier of the present invention having the above effects can be used for various purposes. For example, it can be used as a fluidity improver, a lubricant, a paintability improver, a crystallization promoter, a Wfj impact improver, a filler dispersant, and the like.

Claims (1)

[Claims] 1. Block (A) of polymer (a) with affinity for polyamide and block (c) of polymer (c) with affinity for aromatic vinyl polymer (b) and/or polyester (B
) A modifier for resins consisting of a polymer having 2. A reaction product in which the modifier is a polymer having an affinity for polyamide having a terminal amino group and a polymer having an affinity for an aromatic vinyl polymer and/or a polyester having a terminal carboxylic acid group, or A polymer having an affinity for polyamide having a terminal carboxylic acid group, an aromatic vinyl polymer having a terminal group reactive with a carboxylic acid group, and/or
The modifier for resins according to claim 1, which is a reaction product with a polymer having an affinity for polyester. 3. Polymers with affinity for polyamides include ring-opened (co)polymers of lactams with three or more membered rings, copolycondensates of amino acids capable of polycondensation, (co)polycondensates of dicarboxylic acids and diamines, and Claim 1 or 2: The polymer is selected from the group consisting of vinyl polymers containing as a constituent unit a vinyl monomer containing a group having an affinity for polyamide in the molecule.
Modifier for the resin described. 4. Claims 1 to 3 wherein the polymer having affinity for polyester is a polymer selected from the group consisting of a polycondensate of a dicarboxylic acid component and a diol component, a polymer of polycaprolactone, and a (meth)acrylic acid ester. Any of the resin modifiers described.