JPS63301211A - Impact-resistant styrene resin and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a styrene resin excellent in appearance characteristics, impact resistance, etc., by polymerizing a styrenic monomer containing a rubber material by using prescribed amounts of a solvent and an organic peroxide polymerization initiator under specified three-stepped polymerization conditions. CONSTITUTION:A styrenic monomer (e.g., styrene) containing 3-12wt.% rubber material, 25wt.% or less solvent and 0.001-0.2pt.wt., based on 100pts.wt. raw mixture, organic peroxide polymerization initiator are mixed. In the first step, the raw mixture is subjected to bulk polymerization until a polymer in an amount 0.1-1.5 times the weight of the rubber material is produced. In the second step, the bulk polymerization is continued with stirring until the conversion of the total monomers reaches 18-40% whereby the rubber material is dispersed in the polymer in the form of particles. In the third step, the polymerization is effected until a styrenic polymer having a content of the rubbery material of 3-20wt.% is obtained by bulk polymerization and/or suspension polymerization.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides an impact-resistant styrenic resin that imparts impact resistance and improves appearance characteristics by uniformly dispersing a rubbery substance in granular form. The present invention relates to a manufacturing method.

[Conventional technology 1 7 ABS resin, a copolymer resin of crylonitrile, butadiene, and styrene, has excellent oil resistance, rigidity, heat resistance, and impact resistance, and has a good appearance, so it is used in various electrical products and automobiles. It is used as parts and housing products, but since it is made from acrylonitrile, it is inevitably expensive, and there are limits to its use as a general-purpose material.

For this reason, impact-resistant styrene is produced by stepwise polymerization of styrene in the presence of rubbery substances without the use of acrylic monomers. A method for producing fi (oil) has been proposed (Japanese Patent Publication No. 49-7343); It is unsuitable as a material such as

Furthermore, when producing rubber-modified styrene polymer resins, it has been attempted to improve the physical properties by adding polymerization catalysts and chain transfer agents in several portions (Japanese Patent Application Laid-Open No.
Even with this method, there is a limit to the improvement of impact resistance and other physical properties, and it is not possible to obtain a resin comparable to ABS resin.

[Problem to be Solved by the Invention 1] The present invention provides a method for continuously producing a rubber-modified styrenic resin that has excellent impact resistance, heat resistance, and rigidity, and exhibits good appearance characteristics and processing fluidity. It was done for that purpose.

[Means for Solving the Problems] The present inventors have conducted various studies on methods for obtaining rubber-modified styrenic resins having excellent physical properties. By polymerizing in stages while controlling the polymerization rate under specific conditions,
We have found a way to achieve this objective, and based on this knowledge, we have completed the present invention.

That is, the present invention continuously processes a styrenic monomer containing a rubbery substance or a monomer mixture mainly composed of a styrenic monomer in the presence of a solvent using an organic peroxide as a polymerization initiator. In producing impact-resistant styrenic resin by polymerization, (a) the amount of solvent in the raw material mixture should be 25% by weight or less, and the amount of rubbery substance should be 3 to 12% by weight; (b) raw materials. 0.001 to 0.00% per 100 parts by weight of the mixture.
(c) using 20 parts by weight of an organic peroxide, at least a part of which is added to the raw material mixture at the start of the polymerization; Bulk polymerization is carried out until coalescence is formed (d) Furthermore, in the second step, bulk polymerization is continued while stirring until the polymerization conversion rate of all monomers reaches 18 to 40%, and a rubber-like substance is added to the polymer. by dispersing it in particulate form, and (e) by bulk polymerization and/or suspension polymerization in the third step,
The present invention provides a method for producing an impact-resistant styrenic resin, characterized in that polymerization is carried out until a styrenic polymer having a rubbery substance content of 3 to 20% by weight is obtained.

The styrenic monomer used in the production method of the present invention includes:
Examples include styrene, vinyltoluene, p-methylstyrene, t-butylstyrene, and α-methylstyrene.

Further, the raw material monomer used in the method of the present invention may be one mainly composed of a styrene monomer, and may also be used as a mixture of this and a copolymerizable vinyl monomer. Examples of such vinyl monomers include methyl methacrylate, acrylonitrile, and maleic anhydride, which are mixed with the styrene monomer in an amount of 50% by weight or less based on the total monomers. used.

Next, examples of the rubbery substance used in the present invention include polybutadiene, polyisophrene, tyrene-butanoene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene floc copolymer, Examples include taloloprene rubber and styrene-isoprene copolymer.

These may be used alone or in combination of two or more.

These rubbery substances have a concentration of 3 to 12% by weight in the raw material solution.
It is necessary to use it.

When this concentration is less than 3% by weight, the desired impact resistance cannot be obtained, and when it is more than 12% by weight, the solution viscosity becomes extremely high.
It becomes difficult to feed the raw material.

Although the present invention is carried out in the presence of a solvent, any solvent can be used as long as it has a high solubility for the reaction product.

Especially aromatic hydrocarbons, such as toluene, xylene,
Ethylbenzene alone or a mixture of two or more is preferred.

Furthermore, other solvents, such as aliphatic hydrocarbons and dialkyl ketones, may be used in combination with aromatic hydrocarbons to the extent that they do not inhibit the dissolution of the rubbery substance and the polymerization product from the styrenic monomer. can.

It is necessary to use these solvents in an amount of 25% by weight or less. If the amount used exceeds 25% by weight, the polymerization rate will drop significantly, the impact strength of the resulting resin will decrease significantly, and the energy required to recover the solvent will be large, resulting in poor economic efficiency, which is not preferable.

These solvents may be added after the polymerization has progressed and the reaction liquid has become highly viscous, or may be added from the beginning of the polymerization. It is preferable to add 5 to 15% by weight prior to polymerization in terms of quality uniformity and polymerization temperature control.

Examples of the organic peroxide used as a polymerization initiator in the present invention include 2,2-bis(t-butylperoxy)butane, 2,2-bis(1-butylperoxy)octane, and 1,1-bis(t-butylperoxy)butane. (t-butylperoxy)-3,3,
5-trimethylcyclohexane, 1,1-bis(1-butylperoxy)cyclohexane, n-butyl, 4.4
- Peroxyketals such as bis(1-butylperoxy)valate, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis(1-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-trimethyl-2,5-(
Dialkyl peroxides such as (t-butylperoxy)hexyne-3, acetyl peroxide, imbutyryl peroxide, octaphyl peroxide, decamyl peroxide, lauroyl peroxide, 3,5.5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4 - dichlorobenzoyl peroxide, cage - diacyl peroxides such as toluoyl peroxide, heisopropyl peroxydicarbonate, di-2
-ethylhexyl peroxydicarbonate, di-n-
Peroxydicarbonates such as propyl peroxydicarbonate, di-myristyl peroxine carbonate, di-methoxyisopropyl peroxine carbonate, di(3-methyl-3-methoxybutyl) peroxynocarbonate, t-butyl peroxyacetate, etc. ), 1-butylperoxyisobutyrate, sheeptylperoxybivalate, butylperoxyneodeca7ate, cumylperoxyneodeca/ate, E-butylperoxy-2-
ethylhexanony), t-butylperoxy-3.5
．． 5-) Lythylhexanoate, t-butylperoxy7urate, t-7'tylperoxybenzoate,
Di-t-butyldiperoxyisophthalate, 2.5-
:/Methyl-2.5-di(pensoylperoxy)hexane, peroxyesters such as t-butylperoxyisopropyl carbonate, acetylacecent peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3.3.5-)limethylcyclohexanone peroxide, Ketone peroxides such as methylcyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-methane hydroperoxide, 2,5-tsumethylhexane-2,5-dihydroperoxide, 1, There are hydroperoxides such as 1,3,3-tetramethyl-butyl hydroperoxide.

These can be used alone or in combination of two or more.

In the present invention, the amount of organic peroxide used is o. 0.00 to 0.20 parts by weight, and a portion of it must be added at the beginning of polymerization.

In the first step of the production method of the present invention, the amount of the rubbery material is in the range of 0.1 to 1.5 times, preferably 0.3 times by weight, based on the rubbery material.
The styrenic monomer is graft-polymerized until it reaches a range of ~1.2 times.

In this first step, polymerization is carried out so that the rubber-like material becomes below a critical polymerization conversion rate at which it becomes particles due to a phase transition phenomenon.

In the first stage, the temperature is usually 50 to 140°C, preferably 7°C.
It is desirable that the polymerization be carried out at a constant temperature within the temperature range of 0 to 130°C.

At least a part of the organic peroxide added to the production method of the present invention may be added at the start of polymerization (the rest may be added entirely in the first step, or in the second step or , may be added at a later stage.

Then, in the second stage, the reaction mixture obtained in the first stage was
The polymerization reaction is allowed to proceed continuously at a temperature of 0 to 160°C, preferably 60 to 150'C, and the polymerization conversion rate is 18 to 4.
Set to 0%.

At this time, it is necessary to stir the rubbery substance so that the average rubber particle size in each pellet finally obtained is 0.5 to 1.5 microns. Note that the weight ratio of the polymer to the rubbery substance in the system in the second stage becomes 16 or more, and a phase transition occurs at this stage, and almost all of the phase of the rubbery substance becomes particles.

In the first and second stages, chain transfer agents such as mercaptans, α-methylstyrene linear polymer, terbinolene, and antioxidants such as hindered phenols, Hingul V bis7 ether, etc. and hindered trisphenols, such as 2,6-cy-butyl-4-methylphenol, stearyl-β-(3,5-
Sheet-butyl-4-hydroxyphenyl)propionate can be added.

In the production method of the present invention, the polymerization mixture obtained in the second stage as described above is further polymerized in the third stage until a styrenic polymer having a rubber-like substance content of 3 to 20% by weight is obtained. .

The polymerization reaction format in the present invention is that the first and second stages are carried out by bulk polymerization, but the third stage may be either bulk polymerization, suspension polymerization, or a combination of both.

The first, second, and third stages of the present invention may each be performed using one reaction tank, or each stage may be performed using two or more reaction tanks.

In the method of the present invention, it is advantageous to add the chain transfer agent in portions at each stage and conduct the polymerization while selecting the amount added in relation to the amount of decomposed organic peroxide used as a polymerization initiator.

That is, the addition amount Y of the chain transfer agent in the first stage (parts by weight) and the addition amount Y2 (parts by weight) of the chain transfer agent in the second stage are as follows, with respect to the total amount of 100 parts by weight of the raw material mixture:
Selected within the following range.

1.0 ≦ Decomposed amount (parts by weight). For example, as an organic peroxide, 1,1-bis(t-butylperoxy)-3,3--
When 0.04 parts by weight of trimethylcyclohexane is charged in the first stage, the amount of organic peroxide decomposed in the first stage and the second stage is calculated by the following formula.

However, Kd is the decomposition rate constant of 1,1-bis(thi-butylperoxy)-3,3,5-)limethylcyclohexane<sol/1・hr-'K), and the reaction temperature is T('K ), it can be determined according to the following formula.

Kd-6,969X 10' 8exp(-16720
/T) and θ is the residence time (hr).

In addition, regarding the above, calculations were made assuming that the reaction temperature in the first stage was 99°C, the reaction temperature in the second stage was 115°C, and the residence time was 1.2 hours.

In the present invention, by selecting such reaction conditions, a rubber-modified styrenic resin having better impact resistance and appearance characteristics can be obtained.

According to the method of the present invention, the rubbery substance content is 3 to 20% by weight.
, average rubber particle size 0.5-1.5μI, rubber particle size distribution 1.
2-1.4, del content 14-53% by weight, degree of swelling 6-
It is possible to obtain a rubber-modified styrenic resin having a polyurethane rubber-modified styrenic resin having a hardness of 14, excellent impact resistance, process fluidity, heat resistance, and rigidity, and exhibiting good surface gloss.

The rubber-modified styrenic resin thus obtained is blended with antioxidants, colorants, lubricants, fillers, mold release agents, plasticizers, antistatic agents, etc. as desired, and is used for various purposes. be done.

[Effect of the invention 1] By the production method of the present invention, it is possible to obtain a rubber-modified styrenic resin with an excellent overall balance of quality such as impact resistance, appearance characteristics, processing fluidity, heat resistance, and rigidity, and it is suitable for household electrical appliances,
Can be widely used in audio equipment, etc.

[Example] The present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the following measurement method was used.

(1) Measurement of dispersed particle diameter Take a transmission electron micrograph (magnification: 10,000 times) of the resin using an ultra-thin section method.
Obtained by measuring the number of particles of O~2,000.

Since the dispersed particles shown in the electron micrograph are not perfectly circular, the diameter a in the longitudinal direction and the diameter in the width direction are measured, and the particle diameter is calculated using the following formula.

Particle diameter = F concave - Average particle diameter Ds (u) = Σn1Di / Σn1Di
``Particle size distribution Ds/Dn=(Σn1Di'/Σn1Di2
) Σn1Di/Σni) However, ni is the particle diameter Di
is the number of dispersed particles having .

(2) Amount of gel and degree of swelling 200zN toluene is added to 2g of resin and penetrated vigorously for 3 hours to dissolve or swell. Next, after sedimenting the del in a centrifuge, the supernatant liquid is discarded by decantation, and the precipitated del is weighed. The toluene-swollen gel obtained in above) was naturally dried at room temperature for 24 hours, and then dried at 60°C.
Dry for 6 hours under reduced pressure of 3-5 zzHH, cool in a desiccator and weigh. Del content is expressed in weight percent by dividing the weight of dry del by the weight of resin. The swelling index is expressed as the quotient obtained by dividing the weight of toluene swollen del by the dry del weight.

(3) Melt 70-rate (g710 minutes), JIS K
7210 (measured at 200'C, 5kg>.

(4) Izotsu impact strength Measured in accordance with JIS K 7110 (with /mark).

(5) Flexural modulus ^Measured in accordance with STM D790.

(6) Gloss Measured in accordance with JIS 2: 8741 (incident angle 60°).

(7) Heat distortion temperature Measured in accordance with JIS K 6871.

Example 1 The following mixture is continuously fed into a 13β first polymerization reactor (first stage) at a feed rate of 101/hour.

Low-cis polybutadiene rubber (manufactured by Fukkasei, trade name: NF35^S: Mooney viscosity 35 at 100°C) 7.5 parts by weight Styrene 87.5 parts by weight Ethylbenzene 5.0 parts by weight Total 100
Weight part 1.1-bis(t-butylperoxy)-3,3,5-
) Lithimercyclohexane 0.040 parts by weight n-dodecyl mercaptan 0.013 parts by weight Mineral oil 0.5 parts by weight Antioxidant (manufactured by Ciba Geigy: trade name: Il-nox 1076) 0.070 parts by weight First polymerization vessel The temperature was 93° C., and the amount of polymerized product obtained was 0.53 times (weight ratio) the amount of rubber charged. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, and the rubber phase had not yet turned into particles.

Next, a mixture of this rubber graph F liquid and n-dodecyl mercaptan (0,030 parts by weight) was continuously added to 13
The liquid is sent to the second polymerization vessel (second stage) of No. 1. Temperature 112℃
Then, the stirring speed was set to 300 rpm and the rubber particle size was adjusted. The polymerization conversion rate at the outlet was 24.3%.

The second one further includes a third polymerizer of 191, then a third polymerizer of 20
The solution was sent to a fourth polymerization vessel of ρ, and polymerized at a temperature of 128 to 180°C. The polymerization conversion rate at the outlet was 90.4%.

The obtained polymerization reaction solution was introduced into a degassing step, and was treated in a conventional manner.
Volatile components were removed to obtain a cylindrical pellet.

Next, this pellet was injection molded, and the physical properties of the molded product were measured. The results are shown in Table 1.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that the amount of n-dodecyl mercaptan added and the temperature in the first polymerization vessel (first stage) were changed as shown in Table 1. .

The physical properties of this injection molded product are shown in Table 1.

Example 4 As a rubbery substance, high-cis polybutadiene (manufactured by Ube Industries, Ltd.: BR15HB: Mouni viscosity 40 at 100°C)
Example 1 was carried out in the same manner as in Example 1, except that the amount of n-dodecyl mercaptan, the second stage temperature, and the polymerization conversion rate were changed. The physical properties of the injection molded product obtained were measured and the results are shown in Table 1.

Example 5 The same procedure as in Example 2 was carried out except that the amount of rubbery substance charged was changed as shown in Table 1. The physical properties of the resulting resin injection molded product were measured, and the results are shown in Table 1.

Example 6 In Example 5, the polymerization reaction solution obtained in the second polymerization vessel was sent to the 61 third polymerization vessel. The polymerization conversion rate was 41.3% at a polymerization temperature of 131°C.

100 parts by weight of this polymer, 3 parts by weight of tricalcium phosphate and 0.02 parts by weight of sodium dodecylbenzenesulfonate.
0.3 parts by weight of benzoyl peroxide and 0.05 parts by weight of di-t-butyl peroxide were added to this suspension, and the mixture was heated at 80°C for 2 hours.
Polymerization was completed at 110°C for 2 hours and then at 140°C for 3 hours. The obtained suspended particles are filtered,
The material was injection molded as a pellet using dry extruded rock and its physical properties were measured.

The results are shown in Table 1.

Example 7 Amount of rubber-like material, amount of solvent, type of organic peroxide, amount, timing, amount of chain transfer agent, timing,
The same procedure as in Example 1 was conducted except that the amount of mineral oil charged, the temperature of the second polymerization vessel, the stirring speed, and the polymerization conversion rate were changed as shown in Table 1.

The physical properties of the injection molded resin products obtained are measured, and the results are shown in Table 1.

Example 8 In Example 7, the polymerization reaction solution obtained in the second polymerization vessel was sent to a third polymerization vessel with a capacity of 6ρ. The polymerization conversion rate was 41.3% at a temperature of 131°C.

100 parts by weight of this polymer was suspended in 150 parts by weight of water containing 3 parts by weight of tricalcium phosphate and 0.02 parts by weight of sodium dodecylbenzenesulfonate, and in this suspension,
0.3 parts by weight of benzoyl peroxide and 0.05 parts by weight of butyl peroxide were added, and polymerization was completed at 80°C for 2 hours, at 110°C for 2 hours, and further at 140°C for 3 hours. .

The obtained suspended particles were filtered, dried, and injection molded into pellets using an extruder to measure their physical properties. The results are shown in Table 1.

Example 9 Amount of rubber-like material charged, amount of solvent charged, organic peroxide species, amount charged, timing of charging, amount of chain transfer agent charged, charging timing, amount of mineral oil charged, temperature of the second polymerization vessel, stirring speed,
Example 1 except that the polymerization conversion rate was changed as shown in Table 1.
I did the same thing. The physical properties of the resulting resin injection molded product were measured, and the results are shown in Table 1.

Example 10 The same procedure as in Example 1 was carried out, except that the rubbery substance was a styrene-butadiene copolymer (manufactured by Asahi Kasei Corporation: trade name; Tuftin 2000A: 5x rubber content: 75% by weight). The physical properties of the resulting resin injection molded product were measured, and the results are shown in Table 1.

Example 11 At a feed rate of 10.81/hr, the following mixture was fed into 131
The liquid is continuously fed to the first polymerization vessel.

Low-cis borobugudiene (manufactured by Asahi Kasei Corporation: trade name; Asaprene 700A: Mooney viscosity (100°C)) 6.0 parts by weight Styrene 55.5 parts by weight Acrylonitrile 18.5 parts by weight (weight ratio with styrene 75/ 25) Ethylbenzene 20.0 parts by weight
100.0 parts by weight Benzoyl peroxide 0.025 parts by weight 2.6-di-t-butyl 7 ethanol 0.020 parts by weight n-dodecyl mercaptan 0.010 parts by weight Antioxidant (manufactured by Ciba Iggy Co., Ltd.) Product name: Il 7tx 1076) 0.070 parts by weight The temperature of the first polymerization vessel was 94°C, and the obtained polymerization product was 1.06 times (weight ratio) the amount of charged rubber. . Observation using a phase contrast microscope revealed that the rubber phase had not yet become particulate.

Next, this rubber grafting liquid and n-dodecyl mercaptan (
0,030 parts by weight) is continuously sent to the second polymerization vessel No. 131. The temperature is 111'C, the agitation speed is 22 Orpm, and the rubber particle size is adjusted. The polymerization conversion rate at the outlet was 33.6%.

This product was further processed into a 19β third polymerizer, then a 2ON polymerizer.
The liquid was sent to the fourth polymerization machine, and polymerized at a temperature of 120 to 170°C. The conversion rate at the outlet was 73.2%.

The obtained polymerization reaction solution is passed through a devolatilization step, and is evaporated in a conventional manner.
Volatile components were removed to obtain cylindrical pellets.

The physical properties of the obtained pellet and the injection molded product were measured, and the results are shown in Table 1.

Example 12 Example 1 except that styrene-butadiene copolymer (trade name: Tuffden 2000A) was used as the rubbery substance and the amount of benzoyl peroxide charged was 0.02 parts by weight.
Same as 1. The physical properties of the injection molded resin products obtained are measured, and the results are shown in Table 1.

Example 13 As a rubber-like substance, tylene-butadiene copolymer (Asahi Kasei Corporation!!!: trade name: CARIFLEX TR-110) was used.
2: Solution viscosity of 25% toluene solution at 25°C: 1200
centistokes, rubber containing 172u+t%),
The temperature, stirring speed, and polymerization conversion rate of the second polymerization vessel: jS
The procedure was the same as in Example 11 except for the changes shown in Table 1. The physical properties of the obtained resin injection molded product were measured,
Shown in Table 1.

The results of Examples 1 to 13 above are shown in Table 1.

Comparative Example 1 In Example 1, the raw material in which the amount of n-dodecyl mercaptan charged was 0.030 parts by weight was sent to the second polymerization vessel No. 131 without passing through the first polymerization vessel. The temperature was 118°C, the stirring speed was 300 rpm, and the obtained polymerization product was
The amount was 3.2 times (weight ratio) the amount of rubber charged. Phase contrast microscopy revealed white rubber particles in the black polystyrene continuous phase.

The subsequent polymerization steps were the same as in Example 1.

The physical properties of injection molded products of the obtained resin were measured and are shown in Table 2.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the temperature of the first polymerization vessel was 114°C. The polymerization product obtained in the first polymerization step was 1.93 times (weight ratio) the amount of rubber charged. Phase contrast microscopy revealed white rubber particles in the black polystyrene continuous phase. The physical properties of injection molded products of the obtained resin were measured and are shown in Table 2.

Comparative Example 3 The same procedure as in Example 3 was conducted except that the first polymerization step temperature was 123°C and the polymerization conversion rate at the outlet was 44.8%.

The physical properties of injection molded products of the obtained resin were measured and are shown in Table 2.

Comparative Example 4 The temperature of the first polymerization vessel and the second polymerization vessel were each 117°C1.
The temperature was 117°C, and the ratio of the polymerization product obtained in the first polymerization vessel to the amount of charged rubber was 2.96 (weight ratio),
The same procedure as in Example 1 was conducted except that the polymerization conversion rate at the first polymerization step entrance was 45.2%. The physical properties of the injection molded resin products obtained were measured and are shown in Table 2.

Comparative Example 5 The same procedure as in Example 6 was carried out except that the amount of rubber charged was 2.0% by weight. Got it! (The physical properties of the oil injection molded products were measured and are shown in Table 2.

Comparative Example 6 Low-cis polybutadiene (Asahi Kasei) was used as a rubbery substance.
Co., Ltd., product name: NF35A, Mooney viscosity 55), the amount charged was 3% by weight, the amount of ethylbenzene was 9.7% by weight, and 0.05 parts by weight of n-dodecylmekabutane and 4.7 parts by weight of mineral oil was added, and the reaction was carried out by so-called thermal polymerization without adding any organic peroxide. At this time, the temperature of the 1jIJ1 polymerization vessel was 103° C., and the ratio of the obtained polymerization product to the amount of charged rubber was 1.47 (weight ratio). Then the second
The temperature of the polymerization vessel was 130° C., and the stirring speed was 300 rpm. The polymerization conversion rate at the outlet of the reaction tank was 25.3%.

The following steps were performed in the same manner as in Example 1.

The physical properties of the obtained resin injection molded product were measured, and the second
Shown in the table.

Comparative Example 7 Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a styrene-butadiene copolymer (trade name: Yu7den 2000A) was used as the rubbery substance. The physical properties of the injection molded resin products obtained were measured and are shown in Table 2.

Comparative Example 8 The amount of rubbery substance charged was 6.4% by weight, the amount of ethylbenzene charged was 8.0 parts by weight, and mineral oil was 2.0 parts by weight, and further, organic peroxide and chain transfer agent were not added. The reaction was carried out by so-called thermal polymerization.

The ratio of the polymerization product to the amount of rubbery material charged in the first polymerization vessel was 1.05 times (weight ratio), the stirring speed of the second polymerization vessel was 450 rpm, the temperature was 130°C, and the polymerization conversion at the outlet was carried out. The same procedure as in Example 1 was conducted except that the ratio was set to 26.5%. The physical properties of injection molded products of the obtained resin were measured and are shown in Table 2.

Comparative Example 9 In Example 11, the raw material in which the amount of n-dodecyl mercaptan charged was 0.03 parts by weight was not passed through the first polymerization vessel,
The same procedure as in Example 11 was carried out except that the liquid was directly fed to the second polymerization vessel. The polymerization conversion rate at the outlet of the second polymerization vessel is 26.
It was 8%. The physical properties of the injection molded product of the obtained resin were measured and are shown in Table 2.

Comparative Example 10 In Example 12, the raw material in which the amount of n-dodecyl mercaptan charged was 0.03 parts by weight was not passed through the first polymerization vessel,
The same procedure as in Example 12 was carried out except that the liquid was directly fed to the second polymerization vessel. The polymerization conversion rate at the outlet of the second polymerization vessel is 26.
It was 2%. The physical properties of the injection molded product of the obtained resin were measured and are shown in Table 2.

Comparative Example 11 In Example 13, the raw material in which the amount of n-dodecyl mercaptan charged was 0.03 parts by weight was not passed through the first polymerization vessel,
The same procedure as in Example 13 was carried out except that the liquid was directly fed to the second polymerization vessel. The polymerization conversion rate at the outlet of the second polymerization vessel was 29.
It was 4%. The physical properties of the injection molded product of the obtained resin were measured and are shown in Table 2.

Comparative Example 12 In Example 8, the reaction was carried out by so-called thermal polymerization without adding organic peroxide, and the amount of chain transfer agent charged and the ratio of the polymerization product to the rubbery substance were as shown in Table 2. I changed it and went. The physical properties of injection molded products of the obtained resin were measured and are shown in Table 2.

July 29, 1988 Director General of the Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case Patent Application No. 137714 of 1988 2, Name of the invention Process for producing impact-resistant styrenic resin 3, Person making amendments case Relationship with Patent Applicant: 3-1-1 Marunouchi, Chiyoda-ku, Tokyo Idemitsu Petrochemical Co., Ltd. Representative: Mutsumi Hongo 4, Agent: 8th floor, Kawashima Kuninobu Building, 2-2-2 Shinbashi, Minato-ku, Tokyo 6
, Number of inventions increased by amendment 0 7. Subject of amendment: Scope of claims in specification and detailed explanation of invention Y 8. Contents of amendment (1) The scope of claims will be corrected as shown in the attached sheet.

(2) “Organic peroxide” on page 4, line 13 of the specification
Next, add "Or organic peroxide and chain transfer agent".

(3) "Manufacturing method" in line 11 of page 5 will be corrected to "manufacturing method, and," and the following sentence will be added on a new line.

[In the presence of a solvent, a styrenic monomer containing a rubbery substance or a monomer mixture mainly composed of a styrenic monomer is continuously processed using an organic peroxide as a polymerization initiator and a chain transfer agent.] In producing impact-resistant styrenic resin through polymerization, (a) the amount of solvent in the raw material mixture should be 25% by weight or less, and the amount of rubbery substance should be 3 to 12% by weight; (b) raw materials. 0.001 to 0.00% per 100 parts by weight of the mixture.
(c) using 20 parts by weight of an organic peroxide and adding at least a part of it to the raw material mixture at the start of polymerization; (c) organic peroxide and chain transfer agent per 100 parts by weight of the total raw material mixture in the first stage; When the amount of addition of
．． Bulk polymerization is carried out until 5 times as much polymer is produced. (d) Furthermore, in the second stage, all 11
When the amount of organic peroxide and chain transfer agent added to 00 parts by weight is x2 and Y2, 1.0≦X 2 / Y 2≦
4.5 to achieve a polymerization conversion rate of 18 to 40 for all monomers.
% by continuing the bulk polymerization while stirring to disperse the rubbery substance in the form of particles in the polymer, and (e) in the third stage by bulk polymerization and/or suspension polymerization to reduce the rubbery substance content. A method for producing an impact-resistant styrenic resin, which comprises polymerizing until a styrenic polymer of 3 to 20% by weight is obtained. (4) Delete ``Continuous transfer agents, such as mercaptans, 3-methylstyrene linear dimer, terbinolene, etc.'' from the bottom line of page 11 to the second line of page 12.

(5) On the bottom line of page 12, it says, ``Next, when an organic peroxide and a chain transfer agent are used as a polymerization initiator in another invention, the chain transfer agents include mercaptans, α-methylstyrene linear dimer, They are terpinolenes.”
will join.

Claim 1: Continuous polymerization of a styrenic monomer containing a rubbery substance or a monomer mixture mainly composed of a styrene monomer in the presence of a solvent using an organic peroxide as a polymerization initiator. In producing impact-resistant styrenic resin, (a) the amount of solvent in the raw material mixture should be 25% by weight or less, and the amount of rubbery substance should be 3 to 12% by weight; (b) the raw material mixture 0.001 to 0.00% per 100 parts by weight.
(c) using 20 parts by weight of an organic peroxide, at least a part of which is added to the raw material mixture at the start of polymerization;
Bulk polymerization is carried out until 5 times as much polymer is produced. Dispersing the rubbery substance in the form of particles, and (e) polymerizing in a third step by bulk polymerization and/or suspension polymerization until a styrenic polymer with a rubbery substance content of 3 to 20% by weight is obtained. A method for producing an impact-resistant styrenic resin.

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Claims (1)

[Claims] 1. In the presence of a solvent, a styrenic monomer containing a rubbery substance or a monomer mixture mainly composed of a styrene monomer is continuously polymerized using an organic peroxide as a polymerization initiator. (a) The amount of solvent in the raw material mixture should be 25% by weight or less, and the amount of rubbery substance should be 3 to 12% by weight, (b) 0.001 to 0.2 per 100 parts by weight of raw material mixture
(c) using 0 parts by weight of an organic peroxide and adding at least a part of it into the raw material mixture at the start of polymerization;
Bulk polymerization is carried out until a polymer of 0.1 to 1.5 times the weight of the rubber material is produced in the second step. Continue bulk polymerization while stirring until the rubbery substance is dispersed in the form of particles in the polymer;
and (e) by bulk polymerization and/or suspension polymerization in the third step,
A method for producing an impact-resistant styrenic resin, which comprises polymerizing until a styrenic polymer having a rubbery substance content of 3 to 20% by weight is obtained.