JPS60208316A - Production of impact-resistant vinyl aromatic heat- resistant resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having improved impact strength and a heat distortion temperature above that of polystyrene, by adding a mixed monomer of specific composition to a disperse system prepared by dispersing a pelletlike elastomer in water medium, and polymerizing the mixed monomer. CONSTITUTION:(A) 10-50pts.wt. pelletlike or powdery elastomer, preferably styrene-butadiene block copolymer is dispersed in water medium in the presence of a dispersing agent. 90-50pts.wt. additional system consisting of (B) 35- 90pts.wt. alpha-alkylstyrene based monomer, e.g. alpha-methylstyrene, (C) 10-45pts.wt. nitrile based monomer, e.g. acrylonitrile, and (D) 0-55pts.wt. monomer copolymerizable therewith is charged into the resultant disperse system and polymerized to give the aimed resin. The reaction is preferably carried by using a polyfunctional initiator, e.g. di-tert-butyl peroxyhexahydroterephthalate.

Description

[Detailed Description of the Invention] Polymer is known as a general-purpose resin and is used in a wide range of fields. However, because of its low impact strength, it is unsuitable for use in fields where impact strength is required.

Therefore, in order to impart impact resistance strength, it was considered to contain rubber, which is known as t-, high impact polystyrene, and is used in fields where strength is required. 1.
Swords and swords are generally blended with rubber to reduce heat deformation temperature, box +
IID'I') decreased by 16, making it inferior to polystyrene in terms of heat resistance.

In view of these circumstances, the present inventors have developed a high-impact topo IJ.
The present invention was developed as a result of intensive studies to obtain a vinyl aromatic resin that has an impact strength comparable to that of styrene (12) and a heat distortion temperature higher than that of polyethylene.

That is, in the present invention, 10 to 50 parts by weight of an elastomer in the form of particles (pellet or powder) are stirred and dispersed in an aqueous medium in the coexistence of a dispersant, and then 35 to 90 parts of α-argyl styrene thread 7mer, preferably 1 (50 to 85 parts, 10 to 45 parts of nitrile yarn monomer, preferably 15 to 35 parts, and 55 parts of heptamer copolymerizable with these heptamers, preferably 0 to 35 parts, especially 1) Desire-! 1., <i;
! IO time half-life temperature is 60 ~] 2 (1"C polyfunctional initiator (containing multiple -0-〇- bonds: f)
and/or a method for obtaining a resin having the above-mentioned properties by adding 90 to 60 parts of additional yarn made of an azo yarn compound and polymerizing it.

In general, to obtain a resin that has the above-mentioned characteristics.

IW of the type with thread that does not contain elastomer + N of fat
It can be blended with a steamer using the blending method, etc. 1 degree of force is applied, and this unpleasant method does not improve the stretch and impact resistance or requires a large amount of fly elastomer, resulting in an improvement in impact resistance of 1.
1. The heat resistance of this material is often reduced by 11 degrees, making it practically meaningless. Therefore, there is a method in which rubber is dissolved in a liquid and polymerized, as shown in the example of high-impact polyester. 1. In order to obtain a heat-resistant, impact-resistant type resin, α-Furkyrus 100% thread 7-mer is polymerized in bulk or in suspension under the coating of Nidistomer.
3 - Then, a monofunctional peroxide such as that used in the polymerization of thread resin, such as penzoyl peroxide or lauroyl peroxide, is used.1,1 In this case, the polymerization conversion rate is increased. In fact, there is a tendency to not stand up. Further, even if a polyfunctional initiator used in the present invention is used at 1° with the initiator, it will not reach a conversion rate of 5 for practical use unless a 2L + 1L yarn is used in combination. 1s,
In the presence of elastomer α-1 Lucils hand-held thread seven threads
In order to obtain a heat-resistant and impact-resistant type resin by polymerizing the above-mentioned monomer composition 11, and preferably using a specific initiator, it has been found that a sufficient conversion rate can be obtained 1. It was.

First, the elastomer to be used is dissolved in the monomer system to be used, then dispersed in an aqueous medium and polymerized (or, polymerized to some extent in bulk and then transferred to suspension polymerization, or polymerized in a bulk state. In order to complete the process, it is necessary to dissolve the elastomer. It will take time to do so. In addition, when transferring these bath liquids, the viscosity is high and:
Problems occur as much as L. Furthermore, since it must be dissolved, there is a limit to the amount of elastomer that can be used. On the other hand, when carrying out suspension polymerization,
When bulk suspension polymerization is carried out, suspension stability becomes a problem, resulting in the generation of a large amount of scale, the shape of the particles obtained becomes distorted, and furthermore, many liters of water are involved in the beads. It often breaks down.

Therefore, in order to avoid these problems, we conducted a study and found the following results:
Use a particulate elastomer (pellet or powder)12, disperse the elastomer in an aqueous medium containing a dispersant, and then mix the elastomer and initiator system.
By polymerizing with lj 7Jfl L, 61
It has been discovered that it is possible to overcome the above-mentioned drawbacks and to produce a product having the desired physical properties. In particular, according to the method of the present invention, elastomers that swell in monomers but have low solubility can also be easily used. In addition, with this method, there is very little scale (no silica-like particles), and the water content in the particles does not actually decrease.The reason for this is that the nidistomer particles act as seed particles. This is thought to be due to the fact that the monomer easily penetrates into the nidistomer particles.Therefore, the elastomer particles used may be selected depending on the target size.Usually, those with a diameter of 01 to 5 mm are used. It is especially good if

The elastomer used here may be one that dissolves in the monomer system used or one that easily swells.
In particular, the five monomer yarns handled by the present invention (styrene,
Butadiene block polymer II, hydrogenated carbon φ
Butadiene block polymer, N 118 etc. are good, but other EP II M, A 13S, M B
S, polyurethane (soft), sulfonated polyester resin, acrylic rubber, vinyl acetate copolymer, vinyl acetate-carbon oxide copolymer, EP rubber,
Other general diene thread rubber can be used.

The α-alkyl monomer mentioned here is α
- α-Alkylated soup stock such as mesenrusu chireshi, and U
Halogenated phenyl group of njl ilf, fullkylated 1. Includes 1 item. 2l・11
As yarn monomers, 7. Lilonitrile, Bukubukuri [
This includes substituted derivatives of J21-Ril and Hisor. Co-T
Examples of monomers capable of forming a TE compound include vinyl thread monomers such as vinyl acetate, i+f acrylate, methyl methacrylate-l-, styrene, and nuclear-substituted styrene.

The amount of these compounds to be used is 1. In order to avoid chemical properties, the α-Furukyrus 100% thread monomer is 35F? , good 11-(ha 5
It is better to use less than 0 parts and 1 part. If the 1°T is less than 10 parts, the polymerization rate will be slow and the conversion rate will be too low to be of practical use. On the other hand, if it exceeds 45 parts, the molded product will have a strong yellowish tinge, which is disadvantageous.

Good amount and 1. That's 15 to 35 parts. joint i
(f) can be combined with styrene 1, e.g. 1,
-Prusstyrene, ortho-, Parametrus-tv
y, etc.] Nuclear substituted silicon, vinyl acetate, various ill 7-acrylates, various acrylates, meth/711 acid, N-methylmaleimide, and N-phenylmaleimide.

A polyfunctional initiator (- is not particularly limited, but a particularly effective one and 1) have a half-life temperature of 60 to 120°C for 10 hours. D
Monokani, such as ditertiary butyl peroxyhexahytroterephthalate, ditertiary butyl peroxyxahydroisophthalate, 1.1'-ditertiary peroxy 3.3. 5-torinocyclohexane, 2,5-dimethylhexane-2,5-bis(baraurate), 2,5-dimethylhexane-2,5-bis(benzoylbaroxy7)hexane, and trifunctional 2.4 to those of
．． 6-) ++Tertiary Petit Bar Ogishi-1,
Examples include 3,5-troazine. Examples of azo compounds useful in the present invention include 7zobisisobuteronitrile, 2.
2'-azobis-(2,4-dimethylvaleronitrile)
, jimeru 212'-azobisisobuturate, 2-
Examples include phenyl 7zo2,4-dimethousandru, 48-onemethoxypaleroni, lyl, I,I'--tsobiscyclohexane-l-carbonitol, and the like.

When using it, it is possible to use several types together.)
It is also possible to use polyfunctional peroxides and 7zo compounds in combination.

The dispersant used for suspension stabilization is not particularly limited, and any dispersant commonly used in suspension polymerization can be used. For example, as the inorganic dispersion n1, fine particulate inorganic substances may be used. Examples include calcium phosphate, calcium carbonate, magnesium carbonate, and silica. Further, as the dispersant, polyvinyl alcohol, polyhydrolidone, and various other surfactants can be used. These are mixed 1. It can be used as

Next, there is no particular limitation on the timing at which the monomer thread is added to the elastomer dispersion, and the monomer thread may be added at any time until the end of the polymerization.

For example, if you add the entire amount of monomer at once to an elastomer system that is stirred and dispersed in an aqueous medium at room temperature, and then heat it at an external temperature of 1-1000 ml until the polymerization temperature is reached, you can add all of the monomer at once after raising the temperature. (, 1 more is added continuously over a certain polymerization time span 1
．． Alternatively, it may be added in a divided manner. The monomers to be used may be added after mixing]7, or they may be added separately[,
However, additional methods can be adopted depending on the purpose. The method of adding the initiator is not particularly limited.
Possible methods include adding the initiator separately, or adding only the initiator separately.

The present invention will be explained below based on Examples and Comparative Examples.
These do not limit the invention.

Examples 1 to 3, Comparative Examples 1 to 2 In a stainless steel autoclave, 120 parts of water, 0.70 parts of tertiary calcium 11phosphate, 0.01 part of sodium dodecylbenzenesulfonate, and 1 part of smolene/gutadiene block
jmer [Asahi Kasei C stock) i, Trublen T-4t 4G,
Average particle size: 07 sheath, butadiene content: 516 U wt%] was charged in the amount shown in Table 1, and stirred to disperse the elastomer. After that, Table 1 shows 1. A monomer system and an initiator were mixed and charged. And 95℃ - Koge 1 audience 1. Polymerization was carried out for 7 hours at 100°C, and the temperature was further increased to 115°C for 1M.
Post-polymerization was carried out for 5 hours. After that, cooling 1-1
True spherical particles of IJMH were obtained. The amount of residual monomer present in the obtained particles was measured by gas chromatography, and the results are shown in Table 1]. Then heat the rolls at 160°C for 10 minutes. sheet l
Strain and press to heat distortion temperature IT D ']' (1
8.6kg/c-load 1. ]TSK-72(17)
, Notsuchi ITZOD impact strength (,]]TSK-71
Samples for 10 measurements were made and the results shown in Table 1 were obtained.

Table 1-11-3BS: Trublen T-414,0 Nanatsuma-A: 70 parts of α-metal styrene, acryloni!
・Mixed monomer A consisting of 30 parts of hydrogen: peroxyno＼
Hexahydroterephthalic acid ditertiary butyl B: 1,1'-ditertiary peroxy-3,3,5-to1
The 10 o'clock temperature range of 1-mer cyclohexane BPO: benzoyl peroxide A and B is 85°C and 194°C, respectively. In Table 1, there was almost no polymerization scale in Examples 1 to B, and the beads adhering to the walls of the polymerization can and the stirring blade were extremely small. In addition, the moisture in the particles was measured using the Karl Fischer method.1.
As a result, all of them were below 0.2% (water absorption rate).

Comparative Examples 3 to 5 HDT and IZOD were measured in the same manner as Examples 1 to 3 using the copolymer sample polymerized in Comparative Example 1 (ratio -1 and below) by low-reflecting the SBS used in the previous example. , the results shown in Table 2 were obtained.

- 12- Table 2 From the ratio 4[12 of Tables 1 and 2, it can be seen that the impact strength of the blend system does not increase.◎ Comparative Examples 6 to 8 Example 1 to 3 Autoclave in the same way as yarns 1 to 3 Water, tertiary calcium phosphate, and sodium dodecylbenzene sulfonate were charged into the medium, and the mixed threads of SBS, monomer, and starting n1 corresponding to Examples 1 to 3 were mixed into a stirred aqueous medium. The polymer was charged into a system and polymerized in the same manner as in Examples 1 to 3.] Physical properties were measured at 5°. The results are shown in Table 3.

Table 3 In Comparative Examples 6 to 8, it was confirmed that a large amount of scale was generated on the Pft, stirring blades, and can walls.

From Tables 1 and 3, it can be seen that this example has no scale claw width and less water absorption.

Comparative Examples 9 to 11 The chemical composition and initiator wipe were the same as those shown in Examples 1 to 3, and the polymer, monomer, and initiator were charged in the same autoclave, and the mixture was stirred for 1 and 2 hours at 95°C. Bulk polymerization was carried out for a period of time, and then water, 1) tertiary calcium phosphate, and sodium F-decylbenzenesulfonate were charged at 95°C.
Suspend at 115°C for 5 hours.
After polymerization for some time, physical properties were measured and the following results were obtained. The results are shown in Table 4.

Table 4 Comparison of Tables 1 and 4) According to the present invention, the water absorption rate and scale amount are small, and? It is understood that the shape of the resin is good.

Examples 4 to 8, Comparative Examples 12 to 13 Shown in Example 1. :': r+ Instead of S, hydrogenated styrene-butadiene block 11mer (r: ++:
t3F;, manufactured by Char Co., Ltd., 〃Rei 1-n-(] 1,
M 13 SF'Kane Ace T (-
True spherical beads with a particle diameter of 1 to 1.5 were obtained in the same manner as in Example 1, except that 56J was used. When this was used to measure physical properties, the above results were obtained.

- 15 - Table 5 D: Lauroyl peroxide Examples 4 to 8 in Table 5 had almost no scale, the water content was 0.2% or less, and the resin was spherical in shape.

As can be seen from Table 5, it is understood that good results can be obtained even if the type of elastomer is changed.

It can be seen that if the polymerization initiator of the present invention is used, an industrially good polymerization conversion rate can be obtained.

Comparative Example 14 - 16 - Actual/A Example 61 With the elastomer shown above and the monomer composition, m
M, I tried to carry out suspension polymerization, but :: II: H7
2 only swells with the monomer and does not swell in mM, and cannot be used in mM.

From the comparison of Example 6 and Comparative Example 14, it can be seen that the present invention is an extremely useful method that can be applied to elastomers that are insoluble in monomers.

1 patent author Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1 Elastomer in pellet or powder form 10-5
Disperse 0 parts by weight (hereinafter referred to as "parts") in an aqueous medium with a dispersant coat rT-1-, and prepare α-furkyl styrene yarn 7-mer 3.
5 to 911 parts, = ) n-thread monomer lO to 45 parts, monomer capable of copolymerizing IiJ with these monomers 0 to 55
1. Add 90 to 50 parts of an additional system consisting of 1. A method for producing impact-resistant vinyl aromatic heat-resistant resin. 2 With initiator and 1-, the time range temperature during IO is 60-120
2. The manufacturing method according to claim 1, which uses a polyfunctional initiator and/or an azo thread compound at .degree. 3. Multifunctional f3FJ Initiator Cover Oxyhexahydroterephthalic Acid Ditertiary Butylene, Peroxyhexahythate
I isophthalic acid di-tertiary butyl, l,l-di-tertiary peroxy-J3.5-trinolysilohexane, 2
, 4.6- Tritasha + 1-Pute Ruber Oxy-1
, 3, fi - at least one selected from Trianno
The production method according to claim 2. 4.7zo thread compound is 1.1'-azobisshi'/l]J\
Claim 2 which is xane-1-carbonitrile
Manufacturing method described in section. 5. The production method according to claim 1, wherein the α-alkyl monomer is a hit or a mixture of α-alkyl monomer and its nuclear substituted monomer. 6. The manufacturing method according to claim 1, wherein the nitrile yarn monomer is one or a mixture of ronitrile and nitrile. 7. The manufacturing method according to claim 1, wherein the α-furkylstyrene monomer is contained in an amount of 50 to 85% of the total amount of the monomer charged.