JPS6137838A - Shock-resistance improved polybutyrene terephthalate resin forming composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to polybutylene terephthalate resins.

More particularly, the present invention relates to molding compositions containing impact-modified polybutylene terephthalate resins.

In one of its more specific hard points, the present invention incorporates therein an ethylene/propylene/diene rubber highly grafted with copolymers of alpha-substituted acrylates and acrylic acid or methacrylic acid or mixtures thereof. The present invention relates to a molding composition containing as a main component a polybutylene terephthalate resin having excellent impact resistance obtained by.

BACKGROUND OF THE INVENTION Techniques for completely improving the impact resistance of polybutylene terephthalate resins are known. For example, U.S. Pat. Nos. 3,405,198 and 3,76 for improved impact strength.
Polybutylene terephthalate can be functionalized with either acid or ester moieties as taught in No. 9,260, No. 4,327,764, and No. 4,364,280. It can be obtained by melt blending with ethylene monopolymers and copolymers. Additionally, U.S. Patent No. 4
．． No. 3 2 0, 2 1 2 teaches the improvement of polyesters by blending them with polycarbonates and with elastic rubbery acrylate copolymers. Polybutylene terephthalate and styrene/alpha-olefin/styrene triblock polyblends are disclosed in U.S. Patent No. 4.11.
No. 9,607.

And, U.S. Pat. No. 4,172,859 teaches impact modification of polybutylene terephthalate with random ethylene/acrylate copolymers and BPDM rubbers grafted with monomeric ester or acid functional groups. ing.

Problems to be Solved by the Invention The present invention provides yet another method for improving the impact resistance of polybutylene terephthalate resin during molding.

[Structure of the invention]

Means for Solving the Problem According to the invention, a polybutylene terephthalate resin;
an elastomer krafted with a copolymer of alpha-substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof, with a weight ratio of about 40 to about 60, wherein the copolymer is thermodynamically blended with polybutylene terephthalate scales. A moldable composition is provided.

Further, according to the present invention, polybutylene terephthalate resin, α-substituted acrylate, and acrylic acid.

from about 40 to about 60 tons with methacrylic acid or mixtures thereof.
% of a copolymer grafted with an elastomer, wherein the copolymer is thermodynamically miscible with the polybutylene terephthalate;
A method for producing a molding composition is provided, which comprises subsequently molding the resulting blend.

Further, according to the present invention, the continuous phase is composed of a polybutylene terephthalate resin and the dispersed phase within the continuous phase, and the dispersed phase is composed of α-substituted acrylate and acrylic acid, methacrylic acid, or a mixture thereof. 60]ti% of a copolymer, the copolymer being thermodynamically miscible with the polybutylene terephthalate resin and forming part of the continuous phase; There is provided a molding composition characterized in that the elastomer is present in sufficient band to improve the impact resistance of the polybutylene terephthalate resin during molding.

In accordance with the present invention, there is also a dispersed phase comprising an elastomer grafted with a copolymer of alpha-substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof, in a weight ratio of about 40 to about 60, in a continuous phase polybutylene terephthalate resin. the copolymer is thermodynamically miscible with the polybutylene terephthalate resin and forms part of the continuous phase;
A method for improving the impact resistance of a polybutylene terephthalate resin during molding, characterized in that the copolymer-grafted elastomer is present in an amount sufficient to improve the impact resistance of the polybutylene terephthalate resin during molding. provided.

Effect Two or more polymers are said to be thermodynamically miscible when the free energy of mixing is negative, and a mixture of two or more polymers results in a substance that exhibits a single, well-defined glass transition temperature. It can be said that thermodynamic miscibility exists.

The polybutylene lenticulate resin beams used in the examples below were manufactured by Genera Electric Co.
Valox® 3, commercially available from L Electric Company
25 polybutylene terephthalate resin. However, any polybutylene terephthalate homopolymer or copolymer is suitable for use in the present invention, and therefore, as used herein, the term "polybutylene terephthalate resin" refers to polybutylene terephthalate resin. A butylene terephthalate monopolymer, a diacid component selected from isophthalic acid or terephthalic acid, and 1,4-butanediol, ethylene glycol.

It refers to a polybutylene terephthalate copolymer having a diol component that is a mixture of at least two diols: 1,3-propanediol and 2,2-bis-(4-hydroxyphenyl)propane.

The impact modifier used in this invention is an elastomer highly grafted with a copolymer of alpha-substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof. This copolymer exhibits full thermodynamic miscibility with polybutylene terephthalate resin.

The elastomeric component of the impact modifier has random dialkyl or alkylaryl peroxide functionality. Approximately 1~20fi! Side chain allylic system, with content in the range of %
Any elastomer having benzylic or conjugated unsaturation is suitable for use.

Particularly suitable elastomers are the olefin/α-olefin/nonconjugated diene terpolymers commonly known as KEPDM rubber and butyl rubber.

EPDM rubber is preferred.

More specifically, it is suitable for use in the production of EPDM elastomers having random dialkyl or alkylaryl functionality, and PDM rubbers have the structural formula OH2=OHR(
In the formula, R is a hydrogen atom or methyl.

ethyl, n-propyl, isopropyl, etc.). Furthermore, EPDM ZAM ij mainly contains a non-conjugated linear or cyclic diene hydrocarbon that can be copolymerized with the above monoolefin. Examples of suitable non-conjugated linear diene hydrocarbons that can be copolymerized with monoolefins include 1,4-pentadiene, 1,4-hexadiene, and 1,5-hexadiene. Examples of suitable cyclic diene hydrocarbons are bicyclo[2,
2゜1]hebuta-2,5-diene, dicyclopentadiene and tetracyclopentadiene. The most preferred EPDM rubbers are terpolymer structures in which the monoolefins are ethylene and propylene and the nonconjugated hydrocarbon diene is either 1.4-' hexadiene or dicyclopentadiene.

The BPDM rubber must consist of 1 to 15 weight percent nonconjugated diene hydrocarbon and 85 to 99 weight percent monoolefin. Monoolefin.

That is, the preferred ratio of ethylene and propylene is 20/
80-80/20, preferably 35/65-65/35
Must. Ethylene/propylene/ethylidene norsernene is not suitable for the practice of this invention. Methods for making these EpDM rubbers are well known and are described in U.S. Pat. No. 3,000,866 and U.S. Pat.
It is described in detail in No. 867.

Peroxide functionality is imparted to the elastomer as follows. The elastomer in a solvent, preferably about 6
Melts at temperatures ranging from 0 to 80°C. The resulting Zam solution is then treated with an oxidizing agent in the presence of a catalyst. The oxidizing agent is an alkyl or aryl hydroperoxide, most preferably it is t-butyl hydroperoxide. The catalyst is Part ■3. ■tlby again. Selected from any of the metals of the dnb group, the ions to be combined are chosen to promote solubility of the catalyst in the Zam solution. The peroxidation reaction is carried out for about 5 to about 20 hours, preferably at about 60 to about 80°C.
It is carried out at a temperature in the range of .

Suitable solvents for dissolving the elastomer include benzene;
Various aromatic solvents such as ti-methylbenzene, toluene, xylenes, and halogenated tetrabenzenes such as chlorobenzene are included, however, the most preferred are chlorobenzene and t-butylbenzene.

Catalysts used to produce peroxide elastomers are based on metals from groups ①a, ②, Ib, or Bb. Preferred metals are conomalt (Group II) or copper (Group 1 [b
family). Preferred catalysts are conolt(II) acetate,
(If), acetylacetonate (U), cononol (2-ethylhexanoate)
IF), conolate naphthenate (formerly, copper(I) acetate,
Copper chloride CI), copper acetylacetonate (I), copper naphthenate (1,) or copper ethylacetoacetate (1).

Most preferred (ethyl acetoacetate) (n)
It is. The most preferred are acetylacetonate conomolt (formerly, naphthenate conomolt (■), copper(I) acetate
, copper(I) chloride and copper(1) acetylacetonate.

Peroxide elastomers prepared in the manner described above typically exhibit a peroxide functionality of 0.05 to 0.1% by weight;
This results in a grafting of 40 to 6 Q of the copolymer matrix.

The copolymer matrix grafted to the elastomer component contains 70 to 95 degrees of substituted acrylate monomer and 5
Consisting of ~30% acrylic acid, methacrylic acid or mixtures thereof. A preferred composition is 70-90% alpha-substituted acrylate monomer and 10-30% methacrylic acid. Copolymer matrix molecular weight is 50,000-50
0,000, preferably 50,000-250,000
Must.

The α-substituted acrylate monomer can be selected from ethyl methacrylate, n-propyl methacrylate or isopropyl methacrylate. Most preferred is ethyl methacrylate.

The resulting elastomer-2-copolymer matrix is comprised, by weight, of about 50 to 90% elastomer and about 10 to about 50% copolymer matrix. The most preferred composition is about 50% to about 70% elastomer and about 50% to about 30% copolymer matrix.

The molding composition according to the invention is approximately 99% by weight.
~about 50% polybutylene terephthalate resin and about 1
~50% elastomer-2-copolymer matrix. Preferably, the molding composition has a molecular weight of about 95 to about 60
Polybutylene terephthalate resin and about 5 to about 40
% elastomer, consisting of a tomer-f-copolymer matrix.

x 5 , A preferred stabilizer is Ethanox.
x) (registered trademark) 330 [Eth-yl
Corp,))(1,3+5-)Listyl-2,4
゜6-t]Nos(3,5-di-tert-butyl-4-
hydroxybenzyl)benzene] and Mark
) (registered trademark) 2112 [Lightcoken Chemical Co., Ltd. (Wi
tco Chemical 0orporatjon)
) () 50:50 mixture of lith(2°4-tert-butylphenyl)phosphite].

The molding compositions of the present invention can be molded using conventional molding equipment, and the molding compositions may also contain fillers, processing aids, pigments, mold release agents, etc., depending on the purpose for which they are commonly used. Other ingredients may also be included, such as. Fillers can also be used in amounts sufficient to provide reinforcement, such as titanium dioxide, potassium titanate and titanate whiskers, glass flakes and chopped glass fins.

〔Example〕

The following examples illustrate the invention.

Evaluation of material properties was performed based on the ASTM standard test described below. Flexural modulus (D-790), tensile strength D
-638), elongation (D-648), notched Izot (D-256) and D'rUL [deflection temperature under load, 2
/8" at 64 psi (18,56kp/i)
3,18wn), D-648:]. Gardner (gar)
dner) The falling weight index is 1-”/4” (3,1
8 cm ) diameter orifice and 8 lb (3,61 V
),"/2' (1,27 cm ) diameter weights. The glass transition temperature, melting temperature and heat of fusion were determined by differential differential calorimetry.

Example 1 This example demonstrates the preparation of a peroxide elastomer suitable for use in the present invention.

20Of ethylene/propylene/dicyclopentadiene (EPDM) terpolymer was dissolved in 2700F of chlorobenzene in a resin reaction kettle. Solution at 70℃
EPDM Samha was easily dissolved in 3.5 hours.

To the resin kettle was added 12Of a solution of 40% anhydrous t-butyl hydroperoxide in toluene. (This solution was published in K.P. Sharpless et al., Journal of Fist Organic Fist Chemistry - (K*B,
5harpress et al, Jou
rnal of Or -ganic Chem
was prepared by extracting a 70'% aqueous solution of t-butyl hydroperoxide with toluene according to the method described by J. Istry), 1983, 48.3607).

Immediately after addition of the hydroperoxide solution, 20 t of 6
% conolate solution in mineral spirits as naphthenic conolate (■) and 22-1,7f acetylacetonate solution dissolved in tetrahydrofuran)
(II) was added. The reaction mixture was heated at 70-72°C.
Holds time. The EPDM rubber was dried under vacuum at 25°C, then dissolved in toluene and precipitated a second time into methanol. The peroxide rubber was vacuum dried at 25° C. for 48 hours. The content of peroxide functionality in BPDM rubber is 1
It was 1067pp.

Example 2 Approximately 2009 peroxidized EPDM rubber having 1067 ppm peroxide functionality was prepared according to the method of Example 1. This 200t of peroxidized EPDM was then heated to 500f at 60°C in a 3 bind (1,7t) pressurized reactor.
of chlorobenzene.

The reactor was charged with 200 r'l of a comonomer mixture consisting of 164 g of ethyl methacrylate and 36 V of methacrylic acid. The reactor was heated to 140°C for 4.5 hours. The resulting polymer mass was precipitated into a 4-fold excess of methanol using a Waring blender.

The resulting polymer pellets were vacuum dried at 110°C. The total amount of BPDM-9-ethyl methacrylate/methacrylic acid (EMA/MAA) recovered was 388 g (97%).

The final composition is 52 parts EPDM and 48 parts BMA/MA.
, it was A.

The composition of EMA/MAA was: 82% ethyl methacrylate and 18% methacrylic acid. 259 EPD
Mr-BMA/MAA with methyl ethyl ketone at 170%
When subjected to time Soxhlet extraction, the peak molecular weight was 197.
,500: Mw of 242,300 and 134.00
6,8f ungrafted EMA/MA with Mn of 0
It turned out to be A (56chi).

The content of EMA/MAA grafted onto the EPDM rubber was 44%. Grafted and non-grafted BMA
/MAA both glass transition temperatures were 120°C.

Example 3 This example illustrates the utility of EPDM-f-BMA/MAA as an impact modifier for polybutylene terephthalate resins.

Three molding compositions having the formulations shown in Table 1 were prepared, and 1.5% by weight each of Mark® 2112Wi inhibitor and Ethanox were added.
ox) 330 antioxidant.

The mparaboloids were extruded, pelletized, and specimens were injection molded for property analysis. The obtained property values are shown in Table 1.

The above data indicate that thermodynamic miscibility exists between the amorphous regions in the EMA/MAA copolymer and PBT resin. Additionally, the data shows that the molding compounds of the present invention have excellent impact and heat resistance.

From the above description, it will be apparent that various modifications may be made to the invention. However, these are considered to be within the scope of the present invention.

Agent Patent Attorney Masaaki Aki Sawa 1 believer

Claims (1)

[Scope of Claims] (1) comprising an elastomer grafted with a polybutylene terephthalate resin and a copolymer of α-substituted acrylate and acrylic acid, methacrylic acid, or a mixture thereof in an amount of about 40 to about 60% by weight; The copolymer is a moldable composition that is thermodynamically miscible with polybutylene terephthalate. (2) The composition according to claim (1), wherein the polybutylene terephthalate resin is a monopolymer. (3) The composition according to claim (1), wherein the polybutylene terephthalate resin is a copolymer. (4) The elastomer is ethylene/propylene/1,4
The composition according to claim (1), which is -hexadiene. (5) The composition according to claim (1), wherein the elastomer is ethylene/propylene/dicyclopentadiene. (6) The composition according to claim (1), wherein the elastomer is butyl rubber. (7) the α-substituted acrylate or ethyl methacrylate;
The composition according to claim 1, which is selected from the group consisting of n-propyl methacrylate and isopropyl methacrylate. (8) The composition according to claim (4), wherein the elastomer is grafted with an ethyl methacrylate/methacrylic acid copolymer. (9) The composition according to claim (5), wherein the elastomer is grafted with an ethyl methacrylate/methacrylic acid copolymer. (10) The composition according to claim (6), wherein the elastomer is grafted with an ethyl methacrylate/methacrylic acid copolymer. (11) Claim No. 1 containing a reinforcing filler (
The composition described in item 1). (2) the copolymer-grafted elastomer has about 1 to about 5
The composition of claim 1, wherein the polybutylene terephthalate resin is present in an amount ranging from about 50 to about 99 percent by weight. (13) forming a blend of a polybutylene terephthalate resin and an elastomer grafted with about 40 to about 60 weight percent copolymer of alpha-substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof; A method for producing a molding composition, characterized in that the copolymer is thermodynamically miscible with a polybutylene terephthalate resin, and the resulting blend is then molded. (14) The method according to claim (13), wherein the blend is molded in contact with a reinforcing filler. (15) a continuous phase consisting of a polybutylene terephthalate resin and a dispersed phase that is an elastomer grafted with about 40 to about 60% by weight copolymer of alpha-substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof; The copolymer is thermodynamically miscible with the polybutylene terephthalate resin and forms part of the continuous phase, and the copolymer-grafted elastomer improves the impact resistance of the polybutylene terephthalate resin during molding. A molding composition characterized in that it is present in an amount sufficient to. (16) α in the continuous phase polybutylene terephthalate resin
Incorporating a dispersed phase consisting of an elastomer grafted with about 40 to about 60 weight percent copolymer of substituted acrylate and acrylic acid, methacrylic acid, or mixtures thereof, the copolymer being thermodynamically combined with polybutylene terephthalate resin. the copolymer-grafted elastomer is present in an amount sufficient to improve the impact resistance of the polybutylene terephthalate resin during molding. A method for improving the impact resistance of polybutylene terephthalate resin during molding.