JPS62241913A - Substituted imide-modified, low-molecular weight polyolefin and its use - Google Patents

Abstract

PURPOSE:To obtain an additive useful for improving the moldability of an aromatic polymer without detriment to its heat resistance, comprising a specified modified low-MW polyolefin specified in the content of a component and an intrinsic viscosity. CONSTITUTION:A modified low-MW polyolefin having the following content of a component and the following intrinsic viscosity is prepared by grafting an N-hydrocarbyl group-substituted unsaturated carboxylic acid imide upon low-MW polyolefin. Said content refers to the content of the N-hydrocarbyl group-substituted unsaturated carboxylic acid imide component units in the modified low-MW polyolefin which in the range of 5-90wt%. Said intrinsic viscosity [eta] is in the range of 0.06-1.2dl/g. It is preferable that the low-MW polyolefin used have an intrinsic viscosity in the range of below 1.2dl/g as determined in decalin solvent at 135 deg.C. As the aromatic polymer used, a styrene resin, especially, ABS is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a specific modified low molecular weight polyolefin and an additive for aromatic polymers comprising the modified low molecular weight polyolefin.

[Conventional technology]

Thermoplastic aromatic polymers such as polyester resin, ABSIt resin, and ASl11 resin are molded by injection molding, blow molding, extrusion molding, and various other molding methods. As the molecular weight of these aromatic polymers increases, the melt viscosity generally increases, resulting in a decrease in fluidity during melt molding and poor lubricity.

In addition, when taking out the molded product from the mold during molding of aromatic polymers, it is easy to mold it to make it easier to mold it. I also apply Haku. However, when molded products are applied to parts such as precision machines and electrical appliances, it is often not allowed to provide a draft angle. As a result, if the shape of the molded product is complex, there are restrictions on the position and size of the protruding bin.

This method has the disadvantage that it is difficult to take out the molded product, which increases the frequency of damage to the molded product. Various attempts have been made to improve the lubricity or mold release properties of these aromatic polymers during molding.

For example, methods include blending aromatic polymers with higher fat sources, higher fatty acid amides, metal salts of higher fatty acids, higher fatty acid esters, liquid paraffin, wax, etc., or applying a mold release agent such as silicone oil to the mold. is proposed. However, in the method of blending the lubricant into an aromatic polymer, a large amount of the lubricant must be blended in order to improve type IIi properties.

As a result, there were problems such as a decrease in the mechanical strength of the aromatic polymer composition. In addition, the method of applying a mold release agent makes the molding operation complicated.

There are disadvantages such as often impairing the appearance and weld strength of the molded product.

In response to such problems, the present applicant has previously published Japanese Unexamined Patent Publication No. 57-1
No. 47533 - JP-A No. 59-A7258, JP-A No. 6-O
188j53, it is proposed to blend a styrene compound grafted polyolefin wax or the like into an aromatic thermoplastic resin.

It is desirable to further improve the heat resistance of the blended aromatic thermoplastic resin. As described above, in recent years, as the above-mentioned thermoplastic aromatic resins have been used in applications where heat resistance is strongly required, such as automobiles, there has been a strong preference for heat resistance. In response to this trend, there is a method of molecular design by changing one kind of monomer so as to increase the heat resistance of the fat, but generally as the heat resistance increases, the moldability often deteriorates significantly. For this reason.

There is a need for a better compounding agent that solves the above problems without causing a decrease in heat resistance.

In view of the above-mentioned current situation, the present inventors further investigated compounding agents and found that a specific modified low molecular weight polyolefin is novel and that compounding it is effective in solving the problem.1 The present invention I was able to complete it.

Note that JP-A-55-790 proposes an embodiment in which an unsaturated α-olefin-maleic acid imidophore polymer is used as a lubricant for molding of thermoplastic plastics; It is a former copolymer, and the copolymerization component units are also different from those of the present invention. Moreover, when the copolymer is added to an aromatic thermoplastic resin, 1
This had the disadvantage of lowering the heat resistance of m-fat.

Furthermore, in Japanese Patent Publication No. 51-43055, etc., a modified polyolefin is used for an adhesive layer between nylon and polyolefin, which is a different application from the present invention, and examples of the modified polyolefin include N-7 2-22 maleimide grafted polyolefin, etc. Although the recommended amount of grafting is smaller than that of the present invention, such a material cannot be used in the present invention as described later.

[Summary of the invention]

The present invention is a modified low molecular weight polyolefin obtained by grafting an N-hydrocarbon group-substituted unsaturated carboxylic acid imide onto a low molecular weight polyolefin, the N-hydrocarbon group substituted unsaturated carboxylic acid imide component in the modified low molecular weight polyolefin. The unit content is in the range of 5 to 90% by weight, and the intrinsic viscosity [η] is 0.06 dl/g to 1.2 dl.
The gist of the invention is a modified low molecular weight polyolefin in the range of /H, and an additive for aromatic polymers comprising the modified low molecular weight polyolefin.

[Low molecular weight polyolefin raw material]

The graft-modified low-molecular-weight polyolefin of the present invention is a specific modified low-molecular-weight polyolefin (hereinafter also referred to as kraft-modified low-molecular-weight polyolefin) obtained by graft-modifying a low-molecular-weight polyolefin with a specific monomer. The low molecular weight polyolefin to be subjected to graft polymerization preferably has an intrinsic viscosity (measured at 135°C in a decalin solvent) of -1.2 dA'/g or less.

Although it depends on the reaction conditions and the type of raw material low molecular weight polyolefin, in general, by grafting the above monomer, the intrinsic viscosity of the graft-modified low molecular weight polyolefin is often increased more than that of the raw material low molecular weight polyolefin. Therefore, if a raw material low molecular weight polyolefin of 1.21/g or more is used, the intrinsic viscosity of the graft-modified low molecular weight polyolefin will be 1.2 dl/g or more, causing problems as described below. Also.

The lower limit of the intrinsic viscosity depends on the amount of modification.

Generally, 0.06 d1/g or more is desirable.

Here, the low molecular weight polyolefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-
It is a homopolymer of α-olefin such as pentene and 1-decene, or a copolymer of two or more α-olefins, and has an intrinsic viscosity within the above-mentioned range. For example, polyethylene wax obtained by pyrolysis of high-pressure polyethylene.

High pressure polymerized polyethylene wax obtained by radical polymerization of ethylene at high pressure, ethylene or ethylene and the above α
- Polyethylene wax obtained by medium-low pressure polymerization of olefin in the presence of a transition metal compound catalyst, or a waxy or liquid polymer obtained by copolymerizing ethylene and α-olefin, polypropylene wax,
Examples include poly-1-butene wax, poly-4-methane-1-pentene wax, and polypropylene-4-methyl-1-pentene copolymer wax. Note that the low molecular weight polyolefin herein also includes phthalates of low molecular weight polyolefins.

The oxygen content in this case is usually within 10% by weight.

[Production method of modified low molecular weight polyolefin] The modified low molecular weight polyolefin of the present invention can be produced by grafting an N-hydrocarbon group-substituted unsaturated carboxylic acid imide (monomer) to the above-mentioned low molecular weight polyolefin. As for the unsaturated carboxylic acid which becomes the group constituting the monomer.

For example, maleic acid, tetrahydrophthalic acid, itamozic acid, citraconic acid, nadic acid (endocys-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid), etc. Maleic acid is preferred. Similarly, the hydrocarbon group has 1 to 20 carbon atoms.
straight-chain or branched alkyl group having 4 to 8 carbon atoms;
A cycloalkyl group, an aryl group or a halalkyl group having a prime number of 6 to 26, and among them, an aryl group is preferred. The aryl group is a phenyl group.

Examples include tolyl groups and xylyl groups, among which phenyl groups are preferred. Therefore.

A preferred monomer is N-phenylmaleimide. In addition, these 7-mers can be used not only alone but also as a mixture of two or more kinds.

The grafting reaction can be carried out according to conventionally known methods. For example, the low molecular weight polyolefin mentioned above is exemplified as a preferred monomer.
A method is adopted in which N-phenylmaleimide is reacted with N-phenylmaleimide in a solution or molten state under heating, and the reaction can be carried out in the presence of a radical initiator if necessary.

Radical initiators used in the above reaction include organic peroxides, organic peresters, such as benzoylperoxyr-benzoylperoxide, dicumylperoxide, di-t@rt-benzoylperoxide, 2.5
-dimethyl-2,5-di(peroxybenzoate)hexyne-3,1,4-bis(1,ert-1,000 ruberoxyinpropyl)benzene, lauriloyl peroxide, tart-butyl peracetate, 2,5-dimethyl 1,000-2,5-di(t·rt-p,1,000-ruberoxy)hexyne-5,2,5-dimethyl-2,5-di(tart)
-7'1,000 ruberoxy)hexane, t@rt-butylbenzony), t@rt-butylperphenylacetate-
), t+5rt-gutilpel imp 1000 left, ter
tert-butylperuvalate, tert-butyl peruvivalate, cumyl pervivalate and ta
rt-butyl perdiethyl acetate, other azo compounds such as azobis-isobutyl nitrile, dimethyl acetate. Among these are dicumyl peroxide, di-tart-1,000 ruberoxide,
2,5-dimethyl-2,5-di(tert-1,000 ruberoxy)hexyne-3,2,5-dimethyl-2,5-
Di(tert-butylperoxyphexane, 1.4-
Bis(tert-butylberoxyisopropyl)benzene (D cyfurkyl peroxide is preferred).The reaction temperature is usually in the range of 130 to 300°C, preferably 135 to 250°C.

The modified low-molecular-weight polyolefin of the present invention is a low-molecular-weight polyolefin grafted with the above-mentioned unsaturated carboxylic acid or its anhydride 1, such as maleic acid or maleic anhydride, and the above-mentioned primary amine having a hydrocarbon group 1, such as aniline. It can also be produced by reaction. In this case, the first-stage graft reaction can be carried out in the same manner as in the case of the monomer graft reaction, and the second-stage reaction is carried out using the monomers of the unsaturated carboxylic acids or their anhydrides used for grafting the low molecular weight polyolefin. The first R amine can be added in a molar ratio of 0.8 to 3.0 times, preferably 1.1 to 2.0 times, and the mixture is heated and reacted. The temperature during the reaction is in the range of 150-250°C, preferably 140-220°C.

Note that unreacted carboxyl groups or carboxylic acid anhydride groups may remain in the modified low molecular weight polyolefin molecule.

In any of the above cases, during the graft reaction, other vinyl monomers 1 such as styrene, α-metal styrene, vinyl toluene, etc., (meth)
Acrylonitrile, (methacrylamide, (meth)
Acrylic acid, methyl (meth)acrylate, ethyl (methacrylate).

(meth)acrylic acid n-p1001, (meth)acrylic acid 2
-Dicarboxylic hexyl, vinyl acetate, etc. may be used together. The content of these other vinyl phosphor units is usually 60% by weight or less based on the entire modified low molecular weight polyolefin.

[Properties of modified low molecular weight polyolefin] Content of N-hydrocarbon group-substituted unsaturated carboxylic acid imide component units in the modified low molecular weight polyolefin of the present invention 11 (grafting amount)
must be in the range of 5 to 90% by weight relative to the modified low molecular weight polyolefin, and further in the range of 7 to 6% by weight.
It is preferably in the range of 0 weight i. When the amount of grafting is less than 5% by weight, when added to an aromatic resin, the heat resistance of the resin decreases significantly, and conversely, when the amount of grafting is less than 5% by weight,
If it is larger than this, the softening point of the modified low molecular weight polyolefin will be higher than the molding temperature of the resin, making it difficult to mix with the WI fat and losing its effect as a lubricant, so it is necessary that it be within the above range.

In the modified low-molecular-weight polyolefin of the present invention, the N-hydrocarbon group-substituted unsaturated carboxylic acid/imide component units are grafted at random to the main chain carbons of the low-molecular-weight polyolefin.

Intrinsic viscosity [η] of the modified low molecular weight polyolefin of the present invention
[Measured at 155°C in decalin solvent] is 0.0
It is necessary to be in the range of 6 to 1.2 dg and 7 g, preferably in the range of 0.07 to 1.1.

The intrinsic viscosity of the graft-modified low molecular weight polyolefin is 0.
．． If it is smaller than 06, the aromatic mold release effect will be excellent, but the appearance shrinkage of the molded article will be poor.

Further, the intrinsic viscosity of the modified low molecular weight polyolefin is 1.
If it is larger than 2, even if it is blended with an aromatic polymer, the lubricating effect and mold release effect of the blend will not be observed, and no improvement in moldability will be observed.

[Aromatic polymer]

Examples of aromatic polymers to which the modified low-molecular-weight polyolefin of the present invention can be added as a lubricant or mold release agent include 1, styrenic resins such as polystyrene and ABS, and polycarbonate resins obtained from bisphenol A and phosgene. Polyester resins and polyamide resins such as Chishin Terephthalate and Polybutylene Terephthalate.

1: polyphenylene oxide resin and the like. Among these, styrene resins, especially A
It is preferable to use it for SB.

[Addition method]

The low-molecular-weight polyolefin of the present invention may be added to aromatic polymers on its own, or it may be added together with other components (1), such as stabilizers and fillers (1) and (1) colorants, which are added to synthetic resins as described below. You may. Furthermore, it may be added together with an unmodified low molecular weight polyolefin.

When the graft-modified low molecular weight polyolefin of the present invention is added (compounded) to an aromatic polymer, the addition ratio is in the range of 0.05 to 30 parts by weight based on 100'Iit parts of the aromatic polymer. It is preferable that there be 0, and even 0
．． A range of 1 to 20 parts by weight is particularly preferred. When the addition ratio of the graft-modified low molecular weight polyolefin to 0 parts by weight of the aromatic polymer (A) IQ is less than 0.05 parts by weight, the effect of improving the lubricity effect and the mold release effect of the composition is observed. If the amount exceeds 60 parts by weight, delamination of the molded product will become significant and the balance between mechanical strength and impact strength will be lost. When using the modified low-molecular-weight polyolefin of the present invention, other additives such as dyes, pigments, glass fibers, and carbon black may be added to the extent that they do not impair the purpose of the present invention.

Antistatic agent, heat stabilizer, weather stabilizer, @flame agent.

Calcium carbonate, talc, 5BR1NBR, styrene.
A maleic acid copolymer or the like can be added and blended at the same time.

As a method for blending the modified low molecular weight polyolefin of the present invention with an aromatic polymer, a mixture of the graft modified low molecular weight polyolefin and other additives as necessary is mixed with the aromatic polymer in a Henschel mixer,
- A method of mixing a blender or ribbon blender and then using it directly or kneading and granulating it with a rough extruder etc., Bamba 1
Methods such as melt-kneading and granulation using a 19xa-1 single-screw or multi-screw extruder, kneader, etc., or molding can be adopted.

〔Effect of the invention〕

The aromatic polymer blended with the modified low molecular weight polyolefin of the present invention can be used not only in injection molding but also in molds, blow molding, injection blow molding, compression molding, extrusion molding, single rotation molding, etc.
It reduces adhesion to dies, rolls, etc., improving work efficiency, and improves flowability, resulting in molded products with excellent appearance and dimensional accuracy, while also having excellent heat resistance and mechanical strength. It is useful for industrial parts and 1wL appliance parts.

〔Example〕

Example 1 Intrinsic viscosity 0.0867? /g of high-density polyethylene wax C (trade name: Mitsui Hiwax 110P: manufactured by Mitsui Petrochemical Industries, Ltd.) 350 g was charged into a 14 glass reactor and melted at 140°C. Then heated and dissolved N-
After adding 300 g of phenylmaleimide and 12.0 g of di-tart-butyl peroxide (hereinafter referred to as DTBPO) and reacting by heating for 6 hours, the mixture was heated for 5 m in a molten state.
m Hg vacuum for 1 hour to remove volatiles;
It was then cooled. The amount of N-phenylmaleimide grafted in the obtained N-phenylmaleimide-grafted polyethylene wax (hereinafter referred to as GR-1) was 44 g in 100 g of N-7 dinymaleimide-grafted polyethylene wax. Also, the intrinsic viscosity of GR-1 is 0.3
The GR-1 and heat resistance A were 3417g.
After tri-blending fiS (trade name Stylac-185, manufactured by Asahi Kasei Corporation) at the ratio shown in Table 1,
The mixture was granulated using a 5ff1mφ extruder (temperature set at 220°C).

The granulated sample was made into a size of 200x200x1mm using a compression molding machine.
A square plate was formed.

In addition, test pieces were molded according to each purpose by injection molding 41 (injection pressure 10oO#q, cylinder temperature 260°C). Performance evaluation was performed using the following method.

The results are shown in Table 1.

(1) Flow characteristics: Spiral flow was measured to evaluate the flow characteristics.

Conditions: Injection pressure 1000 kq, cylinder temperature 280
°C, mold temperature 50 °C (2) Heat distortion temperature: Measured by the method of ASTM D 64B (load 66 psi, test piece thickness 6.4 cM).

(3) Mechanical properties: (1) Tensile strength: Measured by the method of ASTM D 63B.

■Bending strength: Measured according to the method of ASTM D 790.

■Izotsu impact strength i Measured by the method of ASTM D 256.

(4) Mold releasability: Depending on the state in which the formed square plate is taken out of the metal frame, the condition in which the square plate can be taken out from the mold without resistance is 5. The condition in which the square plate can be taken out from the mold without resistance is 5, and it cannot be taken out unless the square plate and the metal frame are forcibly peeled off with a razor etc. The evaluation was performed using a 5-point evaluation system, with the state where there was no condition being 1, and the intermediate points being divided into 5 levels.

Example 2 In place of the polyethylene wax with an intrinsic viscosity of 0.08 Ql'/g in Example 1, an intrinsic viscosity f: 3.41 d17 was used.
Using high-density polyethylene wax from Step 1, the amount of N-phenylmaleimide was 50 g, and the amount of DTBP was 2.0 g.
g. The same procedure as in Example 1 was conducted except that the reaction time was 1 hour. Grafting of N-phenylmaleimide in the obtained N-phenylmaleimide graft wax (hereinafter referred to as GR-seal): 100g (7) N-7z
12 g in nilmaleimide graft wax.

Moreover, the intrinsic viscosity of GR-1 was 0.52 J/g.

Example 3 The same procedure as in Example 1 was carried out except that 1 sog of N-phenylmaleimide from Example 1 was taken, 150 g of styrene monomer was added at the same time, and the amount of DTBPO was changed to 10.0 g. [The amount of N-phenylmaleimide grafted in the obtained co-grafted wax of N-phenylmaleimide and styrene (hereinafter referred to as GR-11) was 1
The amount of styrene grafted is 21 g in 100 g of the graft wax.
Met. Also, the intrinsic viscosity of GR-II is 0.29411
It was 7g. ] Performance evaluation is shown in Table 1.

Example 4 In place of polyethylene wax in Example 1, intrinsic viscosity 0
．． The same procedure as in Example 1 was conducted except that 13 d1/g of polypropylene wax was used and the reaction temperature was 170°C. The amount of N-phenylmaleimide grafted onto the obtained 17-phenylmaleimide graft wax (hereinafter referred to as GR-■) is as follows.

There were 45 g in 100 g of N-phenylmaleimide graft wax. Also, the intrinsic viscosity of GR-IV is 0.4
It was 3 dl/g. Performance evaluation is shown in Table 1.

Example 5 Anhydrous maleic-modified polyethylene wax with intrinsic viscosity 0.21 d (1/g) (contains anhydrous maleic m! 110% by weight)
) 350g was charged into 11 glass reactors.

It was melted at 140°C. Next, 65 g of aniline was added dropwise over 1 hour. After the temperature was roughly raised to 200°C and a heating reaction was carried out for 3 hours, the mixture was degassed at 200°C in a vacuum of 5 mmHg for 1 hour to remove water and excess aniline. The content of N-phenylmaleimide groups in the obtained product (hereinafter referred to as GR-V) was 100 g + 7)
The intrinsic viscosity of the GRV was 0.22 dllg. GR-V was blended with ABS in the same manner as in Example 1 and the performance was evaluated. The results are shown in Table 1.

Comparative Example 1 Performance evaluation was performed in the same manner as in Example 1, except that Mitsui Hiwax 110F was used instead of GR-1 in Example 1 as an additive to be mixed with ABS. The results are shown in Table 1.

Comparative example 2

Claims (2)

[Claims] (1) A modified low molecular weight polyolefin obtained by grafting an N-hydrocarbon group-substituted unsaturated carboxylic acid imide onto a low molecular weight polyolefin, the N-hydrocarbon group substituted unsaturated carboxylic acid imide component in the modified low molecular weight polyolefin. The unit content is in the range of 5 to 90% by weight, and the intrinsic viscosity [η] is 0.06 dl/g to 1.2 dl/
Modified low molecular weight polyolefins in the range of g. (2) A modified low molecular weight polyolefin obtained by grafting an N-hydrocarbon group-substituted unsaturated carboxylic acid imide onto a low molecular weight polyolefin, the N-hydrocarbon group substituted unsaturated carboxylic acid imide component in the modified low molecular weight polyolefin. The unit content is in the range of 5 to 90% by weight, and the intrinsic viscosity [η] is 0.06 dl/g to 1.2 dl/g.
An additive for aromatic polymers consisting of a modified low molecular weight polyolefin within the range of .