JPS6019329B2 - Reinforced polypropylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to reinforced polypropylene compositions, particularly reinforced polypropylene compositions containing glass fibers.

It is already known that thermoplastic resins are filled with glass fibers to improve their mechanical properties, heat resistance, etc., and their use as engineering plastics is expanding.

However, the reinforcing effect of the glass fibers of these thermoplastic resins depends on the adhesiveness between the resin and the fibers, and the reinforcing effect will not be exhibited unless the adhesiveness is sufficient. When glass fiber is filled and blended into ordinary polypropylene, polypropylene is non-gutter and highly crystalline, so adhesion to the glass fiber is insufficient, and good mechanical properties and excellent heat resistance are not obtained. I couldn't.

In order to improve this drawback, there is a method of modifying polypropylene with an unsaturated carboxylic acid and/or its anhydride and mixing it with glass fiber to improve adhesion, or a method of mixing modified polypropylene and glass fiber with polypropylene. In the method for improving adhesive properties, the modified polypropylene is obtained by thermally decomposing polypropylene to obtain low molecular weight polypropylene, reacting this with formaldehyde, and further saponifying the resulting methylolated polypropylene, which is further reacted with diisocyanate. A method has been proposed in which polypropylene having isocyanate groups at the terminals is prepared and used. By using these methods, the mechanical properties and heat resistance were considerably improved, but the process was very complicated. The present inventors have completed the present invention as a result of extensive research to improve these drawbacks.

That is, the present invention aims to provide a reinforced polypropylene composition composed of modified polypropylene and glass fiber, which can be obtained by a relatively easy method and has good adhesion to glass fibers and good heat resistance. This objective is achieved by a reinforced polypropylene composition obtained by blending a reaction product of a hydrogenated polymer having at least one hydroxyl group with a polyisocyanate and glass fiber in polypropylene. It was done. The polypropylene composition reinforced in this way has excellent mechanical strength and good heat resistance. The present invention will be explained in detail below.

'1} Specific examples of hydrogenated polymers having at least one hydroxyl group (hereinafter referred to as polyhydroxy hydrocarbon polymers) are as follows.

This polyhydroxy hydrocarbon polymer can be produced by various methods as described below.

For example, polyhydroxy hydrocarbon polymers obtained by completely or partially hydrogenating polyhydroxy gene polymers obtained by various methods, Q-olefins (e.g. ethylene, propylene, isobutylene) and non-conjugated polymers. (Or polyhydroxy hydrocarbon polymers obtained by oxidizing, decomposing, and then reducing a copolymer with a conjugated gene. Among these polyhydroxy hydrocarbon polymers, one molecule of polymer It is necessary that at least some amount of a polymer having one hydroxyl group or two or more hydroxyl groups is contained therein.

Such a hydroxyl group is usually present at the end of a polymer chain. These polyhydroxy hydrocarbon polymers used as raw materials of the present invention refer to those in which the hydrocarbon chains constituting the polymer are completely or partially saturated.

For 1,4 polybutadiene, the hydrogenation percentage is at least 20%, preferably 30% or more.

Since 1,4 polyptadiene has 50% of carbon atoms involved in double bonds in its main chain, it is necessary to reduce this to 40% or less in the present invention.

Although 1,4 polybutadiene has been explained above, 50% of 1,2 bond moieties may be included in the polybutadiene, and even in such a case, among the carbon atoms constituting the main chain, double bonds may be present. It is important that no more than 40% are involved.

However, in the present invention, polybutadienes having more than 50% 1,4 bonds, especially more than 70%, are used as suitable raw materials. Next, specific methods for producing these raw material polyhydroxy hydrocarbon polymers of the present invention will be explained in more detail.

Hydrogenated products of polyhydroxygene-based polymers can be easily obtained by catalytically hydrogenating polyhydroxygene-based polymers in accordance with conventional methods. It can be easily obtained by polymerizing a conjugated gene monomer and another monomer such as a vinyl monomer using a hydrogen peroxide initiator or an azbisisonitrile initiator having a hydroxyl group.

Conjugated diene monomers used in such polymerization include 1,3-butadiene, isoprene, 1,3-bentadiene, 2,3-dimethylbutadiene, etc. Other monomers include the general formula (where RI is a hydrogen atom or an alkyl group, and R2 represents an aryl group, a carboxyl group, an ester group, a pyridyl group, or the like.

), such as styrene, acrylonitrile, acrylic acid, methacrylic acid, acrylate,
Examples include methacrylate and vinylpyridine.
In the case of copolymerization, the content of other monomers in the resulting copolymer is usually 75% by weight or less, preferably 5% by weight.
It is as follows. Examples of azobisisonitrile compounds having a hydroxyl group include 8,8'-azobis(8-cyano-n-propanol) and 6,6'-azobis(6-cyano-n-bentanol). Polyhydroxydi. En-based polymers are also disclosed in, for example, Japanese Patent Application Laid-Open No. 48-2
8595, by reacting an epoxy compound such as a halogen alkylene oxide with a diene-based sliding polymer, and then treating it with protonic acid, or according to the method of Tokokukan Sho 49-3046 No. It can also be produced by a method in which a living polymer is reacted with a halogen alkylene oxide or a polyepoxy compound, and then further reacted with a monoepoxy compound, and then treated with a protonic acid, or by various modifications of these methods. .

The living gene polymer used in these methods is a dialkali metal polymer in which an alkali metal is bonded to both ends of the molecule. Such a forming polymer can be prepared by adding a conjugated diolefin alone or a conjugated diolefin and another monomer represented by the above general formula (1) to an alkali metal or an organic alkali metal compound according to a known method. It can be easily obtained by polymerization in the presence of. Examples of alkali metals used in this polymerization include lithium, sodium, potassium, rubidium, and cesium, and examples of organic alkali metal compounds include naphthalene rust, acetracene rust, biphenyl rust, styrene rust, and styrene rust. Organic bodies of alkali metals such as 1,4-dialkali metal butane, 1,5-dialkali metal pentane, 1,10-dialkali metal decane, 1,2-dialkali metal 1,2-
diphenylethane, 1,4-dialkali metal-1,1,
Examples include dialkali metal hydrocarbons such as 4,4-tetraphenylbutane. Hydrocarbon solvents such as hexane, heptane, benzene, cyclohexane, cyclohexane, toluene, and methylcyclohexane are used to make the living polymerization proceed smoothly.In particular, when the reaction is to be carried out uniformly, the above-mentioned hydrocarbon solvents are used. A mixed solvent of a solvent and a Lewis base is used. As such Lewis bases, oxygen-containing Lewis bases such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, anisole, and ethyl phenyl ether, and nitrogen-containing Lewis bases such as trimethylamine, triethylamine, and dimethylaniline are used. be done.

The thus obtained polymer, which usually has alkali metals attached to both ends, is reacted with an epoxy compound based on the method of each of the above patent applications, and then treated with a protonic acid such as hydrochloric acid, sulfuric acid, or acetic acid. Upon treatment, a polyhydroxygene polymer can be obtained. Epoxy compounds to be reacted include monoepoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and phenyl glycidyl ether; diglycidyl ether of bisphenol A, vinyl cyclohexene diepoxide, and butadiene diethyl ether; Polyepoxy compounds such as poxide, dicyclobentadiene diepoxide, limonene dieboxide, and bis-epoxide of ethylene glycol; and halogenoalkylene oxides (i.e., haloepoxy compounds) such as epichlorohydrin, methylepichlorohydrin, and epibromohydrin. . These epoxy compounds are used in various combinations and in various amounts.

For example, when a living polymer is reacted with a monoepoxy compound in an amount twice or more in mole or more, the epoxy compound is ring-opened and bonded to both ends of the living polymer, and the hydrogen of the hydroxyl group generated by the ring opening is A group in which an atom is substituted with an alkali metal, that is, a 1OM group (M represents an alkali metal)
A polymer having the following is produced, and this -OM group is converted to a hydroxyl group by protonic acid treatment. Furthermore, when a polyepoxy compound or a halogenoalkylene oxide is reacted, the molecular weight and number of hydroxyl groups of the resulting polymer vary depending on the reaction ratio. That is, it is usually 0.5 to 2. These are reacted in a molar range, especially 0.6 to 1.7 times the molar range, but in this case, various polymers in which living polymers are linked are produced,
Since an -OM group is formed in the ring-opened epoxy group, if this polymer is treated with a proton acid, the polymer will have a hydroxyl group at each joint of the IJ Bing polymer unit. Furthermore, if the living polymer is reacted with less than equimolar amount of polyepoxy compound or halogenoalkylene oxide and then reacted with a monoepoxy compound,
-OM groups are formed at each seam and at both ends of the IJ Bing polymer unit of the resulting polymer, and when this polymer is treated with protonic acid, -OM groups are formed at both ends and the middle part of the molecule (at each seam). A polymer having hydroxyl groups is obtained. By hydrogenating polyhydroxygene polymers obtained by the various methods described above, polyhydroxy saturated hydrocarbon polymers used as raw materials of the present invention can be obtained.

For the hydrogenation, commonly used catalytic hydrogenation means can be employed. That is, as the hydrogenation catalyst, a nickel catalyst (for example, Raney nickel), a cobalt, platinum, palladium, ruthenium, or rhodium catalyst, which has been used for a long time, or a mixed or alloy catalyst thereof can be used. These catalysts can be used alone as a solid or soluble homogeneous body, or supported on carbon, silica, quartz, etc. Furthermore, hydrogenation may be carried out using a metal body obtained by reducing a compound containing nickel, titanium, cobalt, etc. with an organometallic compound (for example, trialkylaluminum, alkyllithium, etc.). Molecular hydrogen or a gas containing molecular hydrogen can be used as long as it does not contain any substance that poisons the catalyst. There is no difference in hydrogen pressure whether it is a normal pressure blow or a pressurized system. The temperature is from room temperature to 200°C, preferably below 150°C.
The polyhydroxygene polymer can be used alone or as a solution in a solvent. As such solvents, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, aliphatic carboxylic acids, etc. can be used alone or in a mixed system. As already explained in part, another method for producing the polyhydroxy saturated hydrocarbon polymer used as a raw material in the present invention is to oxidize and separate a copolymer of Q-olefin and other monomers, and then reduce the copolymer. Here are some ways to do it.

For example, if a butyl rubber-based polymer obtained by cationic polymerization of isobutylene and ptadine or 1,3-pentadiene is subjected to ozone decomposition treatment and then reduced with lithium aluminum hydride, a polyhydride can be obtained. Oxypolyisobutylene is obtained. Further, a polyhydroxypolyolefin can be obtained by ozonolyzing a polyQ-olefin having an unsaturated bond obtained by copolymerizing ethylene alone or with a gene in the coexistence of propylene, and then reducing the polyQ-olefin. Legs The "reaction product of polyhydroxy hydrocarbon polymer {1' and polyisocyanate" used in the present invention is prepared as follows. The polyisocyanate used in the present invention includes 2,4
-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3-bitlylene-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, 3
, 3'-dimethylphenylmethane-4,4'-diisocyanate, ethane diisocyanate, propane diisocyanate, butane diisocyanate, thiodiethyl diisocyanate, thiodipropyl diisocyanate,
'-diisocyanate-1,3-dimethylbenzole, '-diisocyanate-1,4-dimethylbenzole, '-diisocyanate-1,2-dimethylcyclohexane, '-diisocyanate-1,4
-dimethylnaphthalene, 1,3-phenyl diisocyanate, naphthalene diisocyanate, biphenyl diisocyanate, 1,3,5-trimethylbenzole-2,4,6-triisocyanate, triphenylmethane-4,4'-4''- Examples include polyisocyanates represented by the following general formula obtained by phosgenating triisocyanates and reaction products of aniline and formaldehyde.

In the above formula, a mixture of about 50% diisocyanate where n=0 and about 50% polyisocyanate where n=1 to 4 is commercially available as crude MDI or PAPI.

The reaction between the polyhydroxy hydrocarbon polymer and the polyisocyanate is performed when the isocyanate group/hydroxyl group (molar ratio) is 1.
It is carried out under larger conditions, the temperature is 20~150oo,
Preferably, it can be carried out at 30 to 100 oo.

The reaction can be carried out by diluting it with a solvent, but it can also be carried out without a solvent (
It is also possible to do this in bulk. Also, even if a catalyst is used,
It is easy to cause the reaction to proceed sufficiently even without a catalyst.
An appropriate value for the above ratio is 1.0 or more and 10 or less. In this reaction, if polyisocyanate is used in excess, it remains as an unreacted product, but this does not have any adverse effects even if it is not removed afterwards. Also,
In the present invention, there is no problem even if part of the polymer '1} coexists with a gen polymer, a vinyl polymer, etc. that does not contain a hydroxyl group.

These do not react with the polyisocyanate and act merely as a diluent or filler. The reaction product obtained in this way has a structure in which one or more isocyanate groups are bonded to a matrix made of a saturated hydrocarbon polymer via a urethane bond, and in the present invention, this reaction product is directly converted into polypropylene. It can be blended with.

In some cases, the reaction product may be further reacted with an active hydrogen compound (blocking agent) to block isocyanate groups present therein, and the blocked product may be blended into polypropylene. In short, the "reaction product of a polyhydroxy hydrocarbon polymer and polyisocyanate" as used in the present invention includes both unblocked products and blocked products. As flocculants, phenol,
Phenols such as p-chlorophenol, p-nitrophenol, and cresol; Oximes such as methyl ethyl ketone oxime, cyclohexanone oxime, acetoxime, and penzophenone oxime; Lactams such as go-caprolactam and pyrrolidone; t-butyl alcohol and diacetone alcohol; imides such as phthalimide, maleimide, and ethyleneimide; mercaptans such as t-dodecyl mercaptan and t-butyl mercaptan; and inorganic substances such as sodium bisulfite and boric acid. Since the above-mentioned blocked product does not have free isocyanate groups, it is easy to handle when blending with polypropylene.

After such a blocked product is blended with polypropylene,
When heated to a high temperature, the isocyanate group is liberated again. Legs The polypropylene used in the present invention is a highly crystalline propylene homopolymer with stereoregularity or a crystalline copolymer of propylene and other Q-olefins.

The crystallinity of propylene homopolymer has a heptane insoluble content of 9.
0% or more is preferably used. In addition, in copolymers with other Q-olefins, the content of Q-olefin is usually 20% or less and the crystallinity is 80% or more.

The melt flow index of these polypropylenes is 0.
．． 0.01 to 50 can be used, but 0.1 to 20 is preferable.

(2) The glass fibers used in the present invention are usually commercially available reinforcing glass fibers, with diameters ranging from several microns to several tens of microns, and are usually assembled in several hundred pieces using a binding agent.

This focusing agent contains a film forming agent, a coupling agent, and others, but it is not limited to the types of these agents, and any one can be selected.

Also, long glass fibers can be used, but
When mixed with polypropylene, chopped strands obtained by cutting this into a predetermined length are suitable. The cutting length of the strand is usually several tens of ribs rather than a few ribs, but one length is more appropriate than two ribs.

The amount of the reaction product of the hydrogenated diene polymer and the polyisocyanate in the reinforced polypropylene composition of the present invention is selected at a ratio that effectively exhibits the properties of the composition of the present invention. 0.1 to 2 parts by weight of
0 part by weight, preferably from 0.5 to 1 part by weight. If the amount of the reaction product is less than this, it is difficult to expect an effect, and if it is too much, not only the effect will be reduced, but it will also be economically disadvantageous. The amount of glass fibers can vary over a wide range depending on the purpose, but is usually between 1 and 5% by weight, preferably between 10 and 4% by weight.

If it is less than this, there will be little effect, and if it is too much, it will be difficult to mix and mold! Dark, the surface of the molded product becomes rough. To prepare the reinforced polypropylene composition of the present invention, it is necessary to mix the components to be blended as uniformly as possible.

For this purpose, Brabender plastographs, Banbury mixers, extruders, high-power screw kneaders,
A kneading machine such as a roll can be used.

The reinforced polypropylene composition of the present invention can be applied to the production of injection molding compounds, the production of sheets by extrusion molding or compression molding, the production of various molded products by vacuum forming, the production of laminates of glass cloth and crystalline polypropylene, etc. can do.

Next, examples of the present invention and production examples of raw materials for the compositions of the present invention (
Reference examples) will be explained, but the present invention is not restricted by these examples unless the gist thereof is exceeded.

Reference Example 1 Production of a hydrogenated product of a gen-based polymer having a hydroxyl group at the end: Capacity 10 In the autoclave, commercially available polyhydroxypolybutadiene [manufactured by Arco (~co) Co., Ltd.; R-4 Group T,
Mn: 3110, (1OH) 0.82 heq/night, cis-1,4: 15%, trans-1,4: 58%, pinyl: 27%] 3 kg, cyclohexane 3k9 and carbon-supported ruthenium (5%) catalyst ( After charging 30M (manufactured by Nippon Engelhard Co., Ltd.) and replacing the inside of the system with purified argon gas, high-purity hydrogen gas was autoclaved and supplied, and heating was started at the same time. It took about 3 minutes to reach steady conditions. ,(
An internal temperature of about 100 qo and an internal pressure of about 50 kg/ were reached.

After maintaining this condition for about 1 hour, the hydrogen reaction was stopped,
The polymer was purified and dried according to a conventional method. As a result of analysis by infrared absorption spectrum, the obtained polymer was confirmed to be a hydrocarbon polymer containing almost no double bonds.

Moreover, the -OH group content of the hydrogenated product was 0.81 meq/night. Reference Example 2 Fifty grams of the terminally functional hydrocarbon polymer obtained by the method of Reference Example 1 was placed in a 200°C three-necked flask purged with inert gas purified by a conventional method and heated to 8,000°C.

When it becomes a complete melt, it becomes liquid diphenylmethane diisocyanate (sold by Kasei Upjohn, trade name = lso).
nate 14 round) 26' was added and held at 8000 for 6 hours while continuing to worship. The flask was cooled under the above-mentioned inert gas atmosphere to obtain a solid reaction product A.

Reference Example 3 A hydrocarbon polymer and a polyisocyanate were reacted in exactly the same manner as in Reference Example 2, and at 8,000 yen, 20 tons of phenol was added, and the rope prayer was continued for another 6 hours.

Thereafter, a solid blocked product B was obtained in the same manner as in Reference Example 2. Reference Example 4 In Reference Example 2, tolylene diisocyanate (manufactured by Kasei Upjohn ■, trade name: TDJIOO) 15.4 was used instead of liquid diphenylmethane diisocyanate 26'.
Reaction product C was obtained in the same manner as in Reference Example 2 except that skin was used.

Examples 1 to 4 Commercially available polypropylene (manufactured by Mitsubishi Yuka, MA-3 (crystallinity 90% or more, melt flow index 10/1)
1, 3, 5, and 7 parts by weight of the above reaction product A were added to 100 parts by weight of glass fiber (Asahi Fiberglass ■), CS 06.411,
3% by weight of chopped strands (6 strands long) were added and kneaded for 5 minutes at 200oC in a Brabender plastograph.

The mixture was then heated at 200°C for 15 minutes at a press pressure of 150 kg.
/ Therefore, a test piece was prepared and a Seod impact test was conducted. (A
STMD-256, notched R=0.1 side) Example 5
, 6 In Example 1, lzod was prepared in the same manner as in Example 1 except that blocked product B was used instead of reaction product A.
An impact test was conducted.

Further, the heat distortion temperature (AST) for the composition of Example 6 was
MD-648, 18.6 kg/c fin) was measured. Examples 7 to 10 An lzod impact test was conducted in the same manner as in Example 1, except that reaction product C was used instead of reaction product A.

Comparative Example In Example 1, a composition containing only polypropylene and glass fiber (3% by weight) was prepared in exactly the same manner as in Example 1, without adding the reaction product of the hydrogenated product of the hydrogenated polymer and the polyisocyanate. It was molded and subjected to a Zod impact test.

The results of Examples 1 to 10 and Comparative Example 1 are shown in Table 1.

Claims (1)

[Scope of Claims] 1. A reinforced polypropylene composition comprising polypropylene blended with a reaction product of a hydrogenated diene polymer having at least one hydroxyl group and a polyisocyanate, and glass fiber. 2 As a reaction product of a hydrogenated diene polymer having at least one hydroxyl group and a polyisocyanate,
The reinforced polypropylene composition according to claim 1, characterized in that a blocked product of the same product is used. 3. The reinforced polypropylene composition according to claim 1, characterized in that diphenylmethane diisocyanate or tolylene diisocyanate is used as the polyisocyanate. 4. A reaction product of a hydrogenated diene polymer having at least one hydroxyl group and a polyisocyanate is added to 100 parts by weight of polypropylene.
The reinforced polypropylene composition according to claim 1, which contains 1 to 20 parts by weight. 5. The reinforced polypropylene composition according to claim 1, which contains 1 to 50 parts by weight of glass fiber per 100 parts by weight of polypropylene.