JPH06100692A - Production of hydroxyalkylated polyphenylene sulfide - Google Patents

Abstract

PURPOSE:To produce the polymer which is expected to be used as a precursor of a compatibilizer for a polymer alloy by a simple method by reacting polyphenylene sulfide with a mercapto compd. or a disulfide compd. CONSTITUTION:The polymer is produced by reacting polyphenylene sulfide with a mercapto compd. of the formula: HS-R<1>-OH or a disulfide compd. of the formula: HO-R<1>-S-S-R<1>-OH (in these formulae, R<1> is a 1-10C aliph. or alicyclic residue provided it may contain an OH or SH group). Thus, the polymer is produced by a simple method without causing the degradation of polyphenylene sulfide. Having highly reactive hydroxyalkyl groups, the polymer is expected to be used as a precursor of a compatibilizer for a polymer alloy by utilizing the reactivity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a poly (phenylene sulfide) containing a hydroxyalkyl group, which is obtained by modifying poly (phenylene sulfide) with a modifier selected from compounds having both a hydroxyalkyl group and a mercapto group or a disulfide group. .

The hydroxyalkyl group-containing polyphenylene sulfide obtained by the practice of the present invention is a resin other than unmodified unfunctionalized polyphenylene sulfide, such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, maleic anhydride. When blended with polypropylene having a polar group such as acid-grafted polypropylene or polyphenylene ether, etc., it reacts with the functional groups of these blended resins and enhances compatibility between resins, and is a resin with high solvent resistance, heat resistance and mechanical properties. Give the product. Therefore, this hydroxyalkyl group-containing polyphenylene sulfide is useful as a modifier for polyphenylene sulfide and as a compatibilizer precursor for polyphenylene sulfide and other resins. In addition, this compound is useful as a precursor for polyphenylene sulfide graft or block copolymers.

[0003]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PPS)
May be abbreviated)) is known as a high melting point heat-resistant resin having excellent fluidity, organic solvent resistance, electrical characteristics, flame retardancy, and the like. However, when used as a molding material, there is a drawback that the degree of polymerization is low and the extrusion stability and molding stability are poor.
Further, since the glass transition temperature is not so high, the rigidity is greatly reduced at high temperatures. Therefore, performance improvement has been carried out by compounding with inorganic fillers such as glass fiber, carbon fiber, talc, silica, etc., but in this case, the appearance of the molded product is deteriorated and warpage is likely to occur in the molded product. There is a problem.

Blending with polyolefins and other engineering plastics, such as polyphenylene ethers, polyesters, polyamides, polypropylene, etc., has been carried out with the aim of remedying these drawbacks. However, in these blends, both polymers are inherently poorly compatible. As a result, the obtained resin product becomes brittle, and its mechanical strength and impact strength are lowered, and it cannot be put to practical use.

For example, polyphenylene ether (hereinafter P
A technique for improving the molding processability and flame retardancy of PPE by blending PPS with PE (may be abbreviated as PE) is disclosed (Japanese Patent Publication No. 56-34032). However, although improvements in molding processability and flame retardancy are seen,
PPE and PPS are inherently poor in compatibility, and such a simple blend system has poor affinity at the interface, phase separation occurs during molding, and a composition having excellent mechanical strength cannot be obtained.

Therefore, some techniques have been proposed which can improve the compatibility of the two. For example, it has been proposed to introduce a functional group into PPE to obtain a modified PPE to improve the miscibility with PPS. In JP-A-64-36645 and JP-A-2-36261, a compound having an ethylenically unsaturated bond and an acid anhydride in the molecule, specifically, maleic anhydride and PPE are melt-kneaded to form an acid-modified PPE. Is used. However, the mechanical strength of the resin composition obtained here is still insufficient in connection with the fact that PPS has no reactive functional group.

In polymer blends, the functional groups of both polymers are generally utilized to produce their graft or block copolymers which are often used as compatibilizers for the polymer blends. However, since PPS does not have a functional group in the molecule, the reaction at the time of blending PPS with a resin having another functional group (for example, polyamide, polyester, etc.) can hardly be expected.

In order to introduce a functional group into PPS, therefore, in JP-A-3-502474 and JP-A-2-75656, an aromatic disulfide having a reactive functional group is used as a modifier to give an amino group or A method of making a PPS containing a carboxyl group is disclosed. However, the modified PPS is very brittle because the molecular weight of PPS decreases.
There are problems to be solved such as giving only. Further, Japanese Patent Laid-Open No. 1-259060 discloses a method for producing a hydroxyalkyl group-containing PPS by melt-kneading PPS and 2-hydroxyethyl acrylate. However, since the modifier has an ester bond in the molecule, heat resistance is improved. There is a problem that it is inferior in sex. Therefore, P containing a functional group
There is a continuing market demand for developing techniques for producing PS, especially PPS containing reactive hydroxyalkyl groups, in a relatively simple manner.

[0009]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a method for producing a hydroxyalkyl group-containing PPS which is extremely miscible with polyphenylene ether, polyolefin, polyester and polyamide. With the goal.

[0010]

The present invention will be described in more detail below. The present invention relates to polyphenylene sulfide and general formula (I) or general formula (II)

[0011]

Embedded image HS—R ¹ —OH (I)

[0012]

HO-R ¹ -S-S-R ¹ -OH (II) (wherein R ¹ represents an aliphatic or alicyclic residue having 1 to 10 carbon atoms, R ¹ represents a hydroxyl group or a mercapto group. It is also possible to include a functional group such as.) With a mercapto compound or a disulfide compound represented by the formula (1).

[0013]

According to the method of the present invention, highly reactive hydroxyalkyl group-containing PPS, which is preferably used in polymer blends and the like, can be easily produced by utilizing the reaction of sulfur radicals and the like. <Polyphenylene sulfide> PPS used in the present invention
Is the general formula (III)

[0014]

[Chemical 5]

A crystalline resin containing a repeating unit represented by as a main constituent element. In the present invention, those comprising the above-mentioned repeating unit or those containing the same as the main component, preferably 80 mol% or more, more preferably 90 mol% or more, are preferable from the viewpoint of physical properties such as heat resistance.

When substantially all of the constituent components of PPS are not composed of the above-mentioned repeating unit, the rest (for example, up to 20 mol%) is copolymerizable, for example, the following repeating unit is sufficient. Can be made.

[0017]

[Chemical 6]

(Wherein Y is an alkyl group, a phenyl group, an alkoxy group, preferably a lower alkyl group).
It is preferable that PS has a substantially linear structure from the viewpoint of physical properties of the molded product. As long as the physical properties are not substantially reduced, for example, a polymerized cross-linked product obtained by using an effective amount of a cross-linking agent (for example, trihalobenzene) at the time of polymerization, or a polymer obtained by heat treatment in the presence of oxygen to cross-link the heat. Crosslinked products can also be used.

This PPS has a melt viscosity at 300 ° C. of 1
00-100,000 poise, preferably 500-5
10,000 poise, more preferably 500 to 20,
The range of 000 poise is preferable. Melt viscosity is 10
When it is less than 0 poise, the fluidity is too high and molding is difficult, which is not preferable. Further, even if the melt viscosity exceeds 100,000 poise, the fluidity is too low, and molding is difficult.

This PPS can be manufactured by any method. For example, a method for producing a polymer having a relatively small molecular weight as disclosed in JP-B-45-3368 and a method for producing a linear polymer having a relatively high molecular weight as disclosed in JP-B-52-12240. Alternatively, it can be produced according to a method of heating a low molecular weight polymer in the presence of oxygen to obtain a crosslinked product, or by making necessary modifications thereto. <Modifier> The modifier used for modifying PPS is a compound having a hydroxyalkyl group and a mercapto group or a disulfide group at the same time in the molecule, and is a compound represented by the following general formula (I) and general formula (II). is there.

[0021]

Embedded image HS—R ¹ —OH (I)

[0022]

HO-R ¹ -S-S-R ¹ -OH (II) (wherein R ¹ represents an aliphatic or alicyclic residue having 1 to 10 carbon atoms, R ¹ represents a hydroxyl group, mercapto It is also possible to include functional groups such as groups.) Specific examples of the modifier include:
Dithioerythritol, dithiothreitol, 2,2'-
Dithiodiethanol, 3,3′-dithiodipropanol, 1,1′-dithiodiglycerol, 1-thioglycerol, 3-mercapto-2-butanol, 2-mercaptoethanol, 1-mercapto-2-propanol,
2,3-dimercapto-1-propanol etc. are mentioned. Particularly preferably, dithioerythritol, 2,2 '
-Dithiodiethanol and 1-thioglycerol are mentioned. <Hydroxyalkyl group-containing PPS> The hydroxyalkyl group-containing PPS can be easily produced by reacting a modifier with PPS in a molten state or in an organic solvent.

The hydroxyalkyl group-containing PPS is prepared by dissolving the PPS and the modifier in an organic solvent in which the PPS can be dissolved or partially dissolved, and the PPS and the modifier (0.1 to 100 parts by weight relative to 100 parts by weight of PPS, It can be easily produced by heating and reacting (preferably 1 to 20 parts by weight) at 170 ° C to 300 ° C. After completion of the reaction, the reaction mixture is cooled to room temperature, and the produced modified PPS is precipitated and precipitated from the solution and filtered. Further, in order to remove the unreacted modifier, the filtered product is washed with a solvent such as acetone, methanol, toluene and the like, and then heated or dried under reduced pressure to obtain a desired hydroxyalkyl group-containing PPS.

The organic solvent used here is the raw material P
Although it is desirable that PS can be dissolved, an organic solvent that can partially swell PPS can also be used.
Specifically, aromatic solvents such as diphenyl, toluene and xylene, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene and chloronaphthalene, N-methyl-2-
Examples include aprotic polar solvents such as pyrrolidone, dimethylimidazolidinone, dimethylacetamide, and sulfolane.

Further, the hydroxyalkyl group-containing PPS of the present invention can be produced by the following melting reaction.
For example, a hydroxyalkyl group-containing PPS is the above-mentioned PPS.
0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight of the modifier with respect to PPS, and then mixed with a twin-screw or single-screw extruder or kneader to obtain a temperature range of 280 to 350 ° C. It is preferably produced by melt-kneading in the temperature range of 290 ° C to 320 ° C.

Produced PP containing hydroxyalkyl group
The amount of the functional group of S is 0.1 to 20% by weight, preferably 0.1 to 10% by weight, as the binding amount of the compound used for the functionalization. If it is 0.1% by weight or less, the reactivity with other resins cannot be said to be sufficient, and if it is 20% by weight or more, the physical properties of the resin are deteriorated and gelation occurs, which is not preferable.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples. Polyphenylene sulfide is made by Topren P
PS (Product name: Topren T-7 or Topren T-
1) was used. High temperature GPC measurement is Senshu Science
VHT-GPC 7000 was used and the column temperature was 21.
At 0 ° C., the mobile phase was carried out using 1-chloronaphthalene.

Examples 1-2 Polyphenylene sulfide (Toprene T-7) 100
After 3 parts by weight of the modifier shown in Table 1 was added to 1 part by weight and uniformly mixed, the mixture was melt-kneaded with a twin-screw extruder at a temperature of 310 ° C. to form a strand, which was cut to obtain pellets. Almost no increase in the melt flow value was observed. 0.5 g of the obtained PPS pellets was dissolved in 20 ml of 1-chloronaphthalene at 220 ° C., and after cooling, 30 ml of methanol was added to cause precipitation, and the obtained polymer was separated by filtration.
After drying, a press sheet was prepared and FT-IR was measured. As a result, absorption attributable to the hydroxyalkyl group was observed at the position shown in Table 1. 191 in advance
The amount of hydroxyalkyl group-containing compound bound to PPS was about 2 by comparing with the calibration curve of FT-IR prepared by the peak ratio using the peak at 0 cm ^{−1 as} an internal standard.
It was found to be wt%.

Examples 3 to 4 Polyphenylene sulfide (Toprene T-1) 100
After 3 parts by weight of the modifier shown in Table 1 was added to the parts by weight and mixed uniformly, a Labo Plastomill manufactured by Toyo Seiki Co., Ltd. was used, and the temperature was 290 ° C. and the rotor speed was 180 rpm.
Melt kneading for a minute. After the kneading was completed, it was crushed by a crusher into particles. The granular sample was reprecipitated in the same manner as in Example 1 to remove the unreacted functionalizing agent, and then the FT-IR was measured. As a result, absorption attributable to the hydroxyalkyl group was observed at the position shown in Table 1. From the FT-IR calibration curve, it was confirmed that the amount of the hydroxyalkyl group-containing compound bound to PPS was about 2% by weight.

Example 5 A mixture of 5 g of polyphenylene sulfide (Toprene T-1) and 0.5 g of the modifiers listed in Table 2 was heated with 100 ml of 1-chloronaphthalene under stirring at 200 ° C. for 7 hours. The solution was cooled and the precipitated polymer was filtered, washed with methanol and dried under reduced pressure at 100 ° C. As a result of measuring FT-IR in the same manner as in Example 1, Table 1
Absorption attributed to the hydroxyalkyl group was observed at the position described in. As a result of GPC measurement, almost no change in molecular weight was observed before and after denaturation. It was confirmed from the calibration curve of FT-IR that the amount of the hydroxyalkyl group-containing compound bound to PPS was about 4% by weight.

Comparative Example 1 Polyphenylene sulfide (Toprene T-1) 100
3 parts by weight of 2-hydroxyethyl methacrylate was added to 1 part by weight and uniformly mixed, and then a melt modification reaction was carried out in the same manner as in Example 3. After reprecipitation and removal of unreacted 2-hydroxyethyl methacrylate in the same manner as in Example 1, FT-
IR measurement was performed. As a result, absorption of the carbonyl group of methacrylate was observed near 1720 cm ^-1 ,
No absorption attributable to the OH group could be confirmed. This is considered to be due to the partial thermal decomposition of 2-hydroxyethyl methacrylate due to the high temperature during the modification.

[0032]

[Table 1]

Application Example 1 Hydroxyalkyl group-containing PPS 70 obtained in Example 4
30 parts by weight of alkoxysilane-containing polypropylene (Rinkron XPM 800H manufactured by Mitsubishi Petrochemical Co., Ltd.) were melt-kneaded with a plastomill manufactured by Toyo Seiki Co., Ltd. for 5 minutes under the conditions of 300 ° C. and a rotor rotation speed of 180 rpm. After the kneading was completed, it was crushed by a crusher into particles. Using a compression molding machine manufactured by Toyo Seiki Co., Ltd.
A sheet having a thickness of 2 mm was formed under the condition of 00 ° C. A part of this sheet was cut out, and the cross section of the resin composition was observed with a Hitachi S-2400 scanning electron microscope.
As a result, it was observed that the alkoxysilane-containing polypropylene was finely and uniformly dispersed in a spherical shape, and the dispersed particle size was about 2 μm, and the Izod impact strength (JIS-K-7
110) was 13.5 kg · cm / cm ² .

Comparative Application Example 1 Unmodified PP was used instead of hydroxyalkyl group-containing PPS.
A sheet was obtained in the same manner as in Application Example 1 except that S (Toprene T-1 manufactured by Topren Co., Ltd.) was used. The alkoxysilane-containing polypropylene in this sheet had an average dispersed particle size of about 50 μm, and the dispersed particle sizes were not uniform, and the compatibility of both resins was insufficient. The Izod impact strength was 7.3 kg · cm / cm ² .

Comparative Application Example 2 A sheet was obtained in the same manner as in Application Example 1 except that the modified PPS obtained in Comparative Example 1 was used instead of the hydroxyalkyl group-containing PPS. The alkoxysilane-containing polypropylene of this sheet had a dispersed particle size of about 10 μm and an Izod impact strength of 10.1 kg · cm / cm ² .

[0036]

According to the method of the present invention, a hydroxyalkyl group-containing PPS can be produced by a simple method without deterioration of PPS as shown in the examples. Hydroxyalkyl group-containing PP obtained by carrying out the present invention
S contains a highly reactive hydroxyalkyl group, and it is expected that the S can be utilized for applications such as a compatibilizer precursor for polymer alloys by taking advantage of its reactivity.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of a hydroxyalkyl group-containing PPS (press sheet) obtained in Example 4.
Absorption due to hydroxyalkyl groups is observed at 3440 cm ^-1 .

Claims (1)

[Claims] 1. Polyphenylene sulfide and general formula (I) or general formula (II) embedded image HS-R ¹ —OH (I) embedded image HO—R ¹ —S—S—R ¹ —OH ( II) (wherein R ¹ represents an aliphatic or alicyclic residue having 1 to 10 carbon atoms, and R ¹ may contain a functional group such as a hydroxyl group or a mercapto group). Alternatively, a method for producing a hydroxyalkyl group-containing polyphenylene sulfide, which comprises reacting a disulfide compound.