DE2044867A1 - Thermoplastic mixed resin and process for its manufacture - Google Patents

Description

DIPL-CHEM. DR. ELISABETH JUNG 8 MUNICH DIPL-CHEM. DR. VOLKER VOSSIUS iiiiJViiSS "

DIPL-PHYS. DR. JÜRGEN SCHIRDEWAHN teleoramm-adbesse: invent / monchem PATENT LAWYERS

20U867

u.z .: P 553 C (vdB / kä) September 10, 1970

5O273S

SUMITOMO CHEMICAL COIiPAUY, LTD., Osaka, Japan

¹¹ Thermoplastic mixed resin and process for its production "

Priority: September 10, 1969, Japan, Kr. 71869/69 November 1, 1969, Japan, No. 87964/69

The invention relates to thermoplastic liischharzc with high Weather resistance, excellent transparency and high Impact strength.

To increase the impact strength of a hard, embrittling poly-J merioats, such as polymethyl methacrylate, are already some processes known. For example, the Japanese patent specification Kr. 13266/1965 mentions a process according to which a polymerizable elastic graft polymer, such as polybutadiene in a hard, embrittling polymer is incorporated. However, the polymer obtained is colored or is unsatisfactory Weather resistance as it contains butadiene.

In order to improve the weather resistance, Japanese Patents Mm. 2186/1959 and 2187/1959 a

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Process in which a saturated elastic polymer instead an unsaturated elastic polymer such as a diene polymer is used. However, the disadvantage occurs here poor compatibility of the saturated elastomeric polymer with a hard, embrittling polymer.

Y / enn especially a polymer with excellent optical properties If properties are desired, there must be good compatibility between a hard, embrittling polymer and an elastic polymer incorporated therein. To achieve a "good" tolerance is a Process known from Japanese Patent 1215/1969, in which a hard, embrittling polymer and an elastic The polymer is kneaded with one another at 16o to 230 C in the presence of an organic peroxide, so that a

Crosslinking reaction takes place with or without another reaction between the molecules of these polymers. However is such kneading for the treatment of large amounts of polymer impractical. In addition, the products are easily stained or discolored.

The object of the invention was to provide a polymer with high impact strength and excellent transparency and good weather resistance to obtain.

It has now been found that this task can be achieved by means of a mixed resin is achieved, which is available from three compositions, i.e., a composition consisting mainly of at least an acrylic acid ester, acrylonitrile and / or styrene, a composition consisting mainly of methyl methacrylate

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with or without at least one acrylic acid ester, and a composition consisting mainly of methyl acrylate, with certain process conditions being observed.

The invention thus relates to a thermoplastic synthetic resin the end

5 to 40 percent by weight of a composition (A) based on the mixed resin, v / obei the composition (A) im essentially from 60 to 90 percent by weight of at least one Acrylic acid ester, 40 to 10 percent by weight of acrylonitrile and / or styrene with 0.01 to 20 percent by weight of a diacetone-acrylamide compound and 5 to 0 percent by weight of a polymerizable crosslinking agent, based on the monomers, 5 to 120 percent by weight of a composition (B), based on the composition (A), the composition (B) being essentially from 40 to 100 percent by weight methyl methacrylate and 60 to 0 percent by weight of at least one acrylic acid ester with 0.01 to 20 percent by weight of a diacetone-acrylamide compound on the monomers, and

the remainder is a composition (C) consisting essentially of 80 J up to 100 percent by weight methyl methacrylate and 20 to 0 percent by weight at least one acrylic acid ester.

The invention also relates to a method for production of thermoplastic mixed resin that featured is through

(1) gradually polymerizing a mixture of monomers accordingly of the composition (A), a monomer mixture corresponding to the composition (B) and a monomer mixture according to the composition (C) in any,

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Sequence and heating of the polymer mixtures obtained in Presence of an organic initiator that generates radicals,

(2) stepwise polymerizing a monomer mixture accordingly the composition (Λ) and a mixture of monomers; "corresponding to the composition (B) in any order, The solid polymer obtained is heated in the presence of an organic initiator which generates free radicals and mixing of the polymer obtained with a copolymer obtained by polymerizing a monomer mixture accordingly of the composition (C) has been obtained, and heating the polymer obtained in the presence of an organic radical delivering initiator or

(3) gradually polymerizing a mixture of monomers accordingly the composition (Λ) and a monomeric device according to the composition (B) in any order, Mixing the solid polymer obtained with a Polymer obtained by polymerizing a mixture of monomers corresponding to composition (C), and The resulting polymer mixture is heated in the presence of an organic initiator which produces free radicals.

As acrylic acid esters, lower alkyl acrylates, such as methyl acrylate, ethyl acrylate or butyl acrylate are used v / earth. Examples of diacetone-acryjamide compounds r.ind Diacetone acrylamide or diacetone methacrylamide.

Examples of useful crosslinking agents are Diolestor an unsaturated .jacid, e.g. ethylene; ·; lyholdiaeryil al ooc "λ'thy ... lenglykoldirnethacrylat, unsaturated alcohol ester of an unsaturated Acid, e.g. allyl acrylate or allyl methacrylate, uiigo-

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BATH ORIGINAL

Saturated alcohol esters of polybasic acids, e.g. diallyl phthalate or triallyl cyanurate, diviny compounds such as divinylbenzene or polyethylene glycol dimethacrylate, or polymers of divinyl compounds.

The proportions of the compositions (A), (B) and (C) and the monomers Components in each composition should be within the

above-specified range are kept to a thermoplastic mixed resin with the aforementioned advantageous Properties. If a parameter does not lie within this range, the creation of the " desired thermoplastic mixed resin is not guaranteed. Accordingly, the content of the composition (A) must be 5 to 40 percent by weight, based on the thermoplastic mixed resin, and the content of the composition (B) 5 to 120 percent by weight, based on the composition (A). The composition (C) makes up the remainder of the thermoplastic mixed resin and can be calculated precisely from the sum of the contents of the compositions Calculate (A) and (B).

In order to achieve excellent transparency, the compositions and the proportions of the monomeric components expediently selected such that the refractive index of the elastic polymer according to the composition (A) '

Refractive indices

the / the hard, embrittling polymer is adjusted according to the compositions (B) and (C).

To ensure a high impact strength in the case of the invention Ilischharz is necessary ee that the elastomeric polymer has a satisfactory gel structure, which

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by controlling the amount of the polymerizable crosslinking agent in connection with the amount of the oiacetone-acrylamide compound can be achieved so that a suitable gel content is formed.

The individual manufacturing processes are described in more detail below. For example, the mixed resin can be prepared by polymerizing a monomer mixture stepwise according to the composition (A), a monomer mixture corresponding to the composition (B) and a monomer mixture corresponding to the composition (C) in any order and by heating of the copolymer obtained in the presence of an organic initiator which produces free radicals. In detail, it can be produced by one of the following processes:

(1) Polymerizing an ionomer mixture according to the composition (A), v / oboi a polymer is formed, polymerizing of a monomer mixture corresponding to the composition (B) in the presence of the abovementioned polymer, wubei a solid polymer is formed, polymerizing a monomer mixture according to the composition (C) in the presence of the solid polymer, resulting in a copolymer, and heating the copolymer in the presence of an organic, Radical generating initiator;

(2) Polymerize a mixture of monomers according to the composition (B) a polymer being distorted, polymerizing a monomer mixture corresponding to the composition (A) in Presence of the above-mentioned polymer, with a solid Polymer arises, polymerizing a monomer mixture

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according to the composition (C) in the presence of the solid polymer, whereby a copolymer is formed, and heating of the copolymer in the presence of an organic radical supplying initiator

(3) Polymerize a mixture of monomers according to the composition (C) whereby a polymer is formed, polymerizing a polymer mixture according to the composition (A) in Presence of the above-mentioned polymer, a solid polymer being formed, polymerizing a monomer mixture accordingly of the composition (B) in the presence of the solid poly | merisats, resulting in a copolymer, and heating the Copolymer in the presence of an organic initiator which produces free radicals; or

(4) Polymerizing a monomer mixture in accordance with the composition (C), resulting in a polymer, polymerizing a monomer mixture in accordance with the composition (B) in the presence of the aforementioned polymer, resulting in a solid polymer, polymerizing a monomer mixture in accordance with the composition ( a) merisats, wherein a copolymer is produced in the presence of the solid poly *, and heating the resulting I-Iischpolynerisats Gegenvart in an organic radical initiator.

In the aforementioned processes, the polymerization can be carried out by means of emulsion polymerization or suspension polymerization processes known per se be performed. In the case of EmuleionGpolyinerization v / ground as emulsifiers anionic surface-active agents, such as salts of higher fatty acids, e.g. sodium stearate, Alkyl sulfates, such as sodium lauryl sulfate, alkylbenzene sulfate

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BATH ORIGINAL

called, v / ie sodium dodecylbenzenesulfonate or dialkyl-sulfo-

suecinnte, or nonionic surfactants, such as Ροζ.Β. Polyäthyionoxi.do.

Iy alkyicnoxjde, / used. As polymerization catalysts can Persulfates, such as potassium persulfate or ammonium persulfate, or peroxides, such as hydrogen peroxide or cumene peroxide, are used will.

In the case of suspension polymerization methods, there are usable Suspension stabilizers polyvinyl alcohol, alkali metal salts of polyacrylic acid or polyacrylic acid, sodium phosphate, Magnesium hydroxide, barium carbonate or barium sulfate. Peroxides, such as benzoyl peroxide or lauroyl peroxide, or azo compounds, v / ie azobisisobutyronitrile, can be used as polymerization initiators be used.

In both cases, common additives, such as chain transfer agents, e.g. n-dodecyl mercaptan, lubricants or plasticizers, e.g. liquid paraffin or n-butyl phthalate, added to ground.

It is necessary that the polymerizations of the three mixtures one after the other in the same polymerization system ο line Take into account the sequence of polymerizations to be carried out. Accordingly, what is generated last forms and grows Polymer on the surface of the particles of the polymer previously produced, usually while in a suitable manner the amount of dispersant ^ is controlled.

As noted above, there are a variety of polymerisation orders possible, Jed.) I should carry out the. · PjIvalorisation a monomer mixture according to the composition

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(C) at the intermediate stage between the. Polymerizations of a monomer mixture according to the composition (A) and a Monoraeren mixture according to the composition (B) or vice versa be avoided.

The purpose of the heat treatment is to complete the reaction of a diacetone acrylamide and to remove the remaining monomers. The temperature for the heat treatment is at best 90 .to 13O ⁰ C. If the temperature is below the lower limit "the reaction takes too long. If the temperature is above the upper limit, a higher pressure ™ and therefore an expensive device is required

Time for heat treatment depends on the particular combination
deposition, but generally ranges from 5 minutes to 8 hours. The heat treatment is carried out in the presence of an organic initiator which generates free radicals, for example benzoyl peroxide, · · ■

Lauroylpcrjxid or Azobisisobutyronitril, or a mixture one

with / other radical-generating initiator with a different Half-life. Such organic, radical-generating initiators can after completion | of the polymerizations are added, Palis and if a at the Polymerizations using organic, radical-generating initiator remains after the polymerizations, the remainder can serve for this purpose. Depending on the type of organic, Free radical initiator can be added before or during the polymerizations.

Furthermore, for example, the thermoplastic mixed resin according to the invention can be used by step-wise polymerizing a monomer mixture

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misciis corresponding to the composition (A) and a monomer mixture corresponding to the composition (B) in any order and heating the solid polymer obtained in the presence of an organic initiator which produces free radicals and
Mixing the resulting copolymer with a polymer which has been obtained by polymerizing a monomer mixture corresponding to composition (C), and heating the resulting polymer in the presence of an organic / free radical initiator. In detail
the mixed resin can be produced by one of the following methods;

(5) polymerizing a monomer mixture in accordance with composition (A), a polymer being formed; Polymerizing a honey-paste mixture according to the composition
(ü) in the presence of the polymer, whereby a solid polymer eirtnteht, heating the solid polymer in the presence
an “organi pohcn,” initiator that delivers radicals, thereby, a. Copolymer is formed, and mixing the liischpolymerisats with such a copolymer, dae by polymerizing
a monomer mixture corresponding to the composition (C) and Erhi t;: en; ieE obtained polymerizate has been obtained in the presence of an organic initiator which produces free radicals; or

(6) Polymerizing a monomer mixture according to the composition (B), resulting in a polymer, polymerizing a monomer mixture according to the composition (A) in the presence of the polymer, resulting in a solid polymer, heating the solid polymer in the presence
One o? 3 organic, radical-generating initiator, creating a

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Copolymer is formed, and mixing of the Misschpolymerisats with such a copolymer obtained by polymerizing a mixture of honors according to the composition (C) and Heating the polymer obtained in the presence of an organic, radical-generating initiator has been prepared.

In this process, the polymerization and the heating can be carried out in essentially the same manner as already described, be performed.

Furthermore, for example, the inventive thermoplastic _; j mixed resin by step-wise polymerizing a monomer mixture according to the composition (A) and a monomer mixture according to the composition (B) in any order, mixing the solid polymer obtained with such a polymer that is obtained by polymerising a monomer mixture according to the composition (C) and heating of the polymer obtained can be prepared in the presence of an organic initiator which produces free radicals. In detail, the mixed resin can be produced by one of the following processes: "(7) polymerizing a monomer mixture according to the composition (A), whereby a polymer is obtained, polymerizing a monomer mixture according to the composition (B) in the presence of the polymer, resulting in a solid polymer, mixing the solid polymer with such a polymer that polymerizing a monomeric mixture in accordance with the Zuoawmensotzung (C) has resulted in a mixed polymer, and heating

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this copolymer in the presence of an organic initiator which produces free radicals; or

(8) Polymerize a mixture of monomers according to the composition (B), whereby a polymer is formed, polymerizing a monomer mixture according to the composition (A) in the presence of the polymer, whereby a solid polymer is formed, mixing the solid polymer with such a polymer Polymer obtained by polymerizing a monomer mixture according to composition (C), whereby a copolymer is formed, and heating of this copolymer in the counterv / kind of an organic radical-producing one Initiator.

In these processes, the polymerization and the heating can be carried out in essentially the same way as already described,

carried out v / earth. ■ -. ··· ■■■ <■ ....... ,. .,

According to the invention, the elastic polymer according to the composition (A) is converted into the solid, embrittling polymers corresponding to the composition (B) and the composition (C) without eliminating the former and creating a partial affinity incorporated. For this reason b <> -

height

the mixed resin obtained sits a / weather resistance, a excellent transparency and high impact strength.

The examples illustrate the invention.

At spie]. 1

75 g butyl acrylate, 22 g styrene, 1 g G.lycol dinothacrylate, 2 ■; Diacetone acrylamide, 0.2 ml lauryl mercaptan, 0.2 g ammonium persul-

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fat, sodium dodecylbenzenesulfonate 5 g and 500 g of deionized water are copolymerized 6 hours at 60 ⁰ C. 30 g of methyl methacrylate, 20 g of butyl acrylate, 2 g of diacetone acrylamide, 0.1 ml of lauryl mercaptan and 0.1 g of ammonium persulfate are added to this latex. The mixture obtained is copolymerized at 60 ° C. for 3 hours. After 3 g of benzoyl peroxide have been added to the product obtained, it is heated ^{to 100 to 102 ° C. for 5 hours.} A latex of the polymer (I) is formed.

Separately, 180 g of methyl methacrylate, 20 g of methyl acrylate, 1.4 g of benzoyl peroxide, 0.6 g of lauryl mercaptan, \ g of sodium polymethacrylate and 400 g of deionized water are copolymerized at 80 ° C. for 5 hours. The copolymer is heated to 100 to 101 ^° C. for 1 hour. There are obtained beads of the polymer (II).

Then 180 g of beads of the polymer (II) are added to the latex of the polymer (I) added. The mixture obtained is salted out with calcium chloride with thorough stirring and washed repeatedly and dried. There are 320 g of thermoplastic mixing | resin with a content of polymer (I) and polymer (II) in obtained a weight ratio of 48:52. It is found that the gel content in the polymer (I) after the heat treatment twice as large as before the heat treatment.

The properties of test pieces obtained from the above Composition have been prepared read: "

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Izod impact strength

(kg.cm/cm2, at 20 C) 6.8

Macrographic transparency transparent and light

bluish

-. Total light transmission in
⁰ Jo at 6 mm thickness 87.8

Opacity in ^r ß> at 6 mm thickness' 12.5

Example 2

4.4 g of sodium polymethacrylate, 1.2 g of monosodium phosphate, 582 g of methyl methacrylate, 18 g of ethyl acrylate, 1.9 ml of lauryl mercaptan, 1.0 g of azobisisobutyronitrile and 1000 g of deionized water are copolymerized at 80 ° C. for 5 hours. Then 206 g of butyl acrylate, 44 g of styrene, 1.3 g of glycol dimethacrylate, 5 g of diacetone acrylamide, 1 g of azobisisobutyronitrile, 1 g of benzoyl peroxide and 500 g of deionized water are added. Copolymerization is carried out at 80 ° C. for 3 hours. 75 g of methyl methacrylate, 25 g of butyl acrylate, 0.9 ml of lauryl mercaptan, 3 g of diacetone acrylamide, 0.5 g of azobisisobutyronitrile and 0.5 g of benzoyl peroxide are also added to the copolymer. The mixture is copolymerized 3 hours at 80 ⁰ C. After the end of the copolymerization, the internal temperature is increased to 100 to 106 ° C. The arm treatment is carried out for 5 hours. 940 g of a thermoplastic mixed resin are obtained.

For comparison purposes, a resin mixture is prepared as follows: 40 parts of ethyl acrylate, 30 parts of butadiene, 30 parts of methyl methacrylate, 1 part ethylene glycol dimethacrylate, 0.2 part lauryl mercaptan, 0.8 part potassium persulfate, 5 parts sodium dioctyl sulfosuccinate and 300 parts of deionized water are copolymerized at 6o C for 5 hours. A butadiene latex is used

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rubber received. The conversion is more than 95 Ά. Separately, 97 parts of methyl methacrylate, 3 parts of ethyl aorylate, 0.5 part of lauryl mercaptan, 0.2 part of potassium persulfate, 1 part of sodium dioctyl sulfosuccinate and 200 parts of deionized water are copolymerized for 3 hours at 70 ° C. It will be a
Obtained latex from methyl methacrylate copolymer. The conversion is more than 98 ^c / °. The latex of methyl methacrylate copolymer obtained in this way is mixed with the latex of butadiene rubber obtained above in an amount of 20 percent by weight of the rubber constituents, salted out with calcium chloride, washed repeatedly and dried. A resin mixture is obtained.

The properties of test pieces made from the thermoplastic mixed resin and the resin mixture are v / ie follows: · · - - · - ·· "· - · - · .. ■ - ..

Thermoplastic
Mixed resin Resin mixture
(Comparison) Notched impact strength
Izod (kg.cm/cm*, at 20 C 5.7 ι
4.0 Macrographic transparency transparent and
slightly bluish transparent and
slightly yellowish Total light transmission
in '/ o at 6 mm thick 89.5 90.0 Opacity in $ at a thickness of 6 mm 5.0 3.0 Flowability (g / 10 min
th, at 210 C) 1.8 0.9 Discoloration
(in sunlight) small amount very large

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Example 3

It is a thermoplastic mixed resin prepared as in Example 2, but using 97 g Methylmethaerylat and 3 g of butyl acrylate, instead of 75 g of methyl methacrylate and 25 g of butyl acrylate.

The properties of test pieces made from this thermoplastic mixed resin are as follows:

Notched impact strength according to Izod 4.0

(kg.cm/cm ² , at 20 ⁰ C)

Total light transmission in 90.5

fo at 6 mm thickness

Opacity in ^r / o at 6 mm thickness. 5.0

Example 4

A thermoplastic mixed resin is produced as in Example 2, but using 60 g of methyl methacrylate and 40 g of butyl acrylate instead of 75 g of methyl methacrylate and 25 g of butyl acrylate.

The properties of test pieces from dicisem thermoplastic Mixed resin are as follows:

Notched Izod impact strength 8.1

(kg.cm/cm ", at 20 ⁰ C)

Total light transmission in ^l: ß> 88.5

at 6 mm thickness

Turbidity in ^c / o at 6 mm thickness 7.0

Example 5

A thermoplastic mixed resin is produced as in Example 1, however, using νJn 61.4 g of butyl acrylut and 35.6 g acrylonitrile instead of 75 g butyl acrylate and 22 g sty-

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BATH ORIGINAL

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rol in the preparation of the latex of the polymer (I).

The properties of test pieces made from this thermoplastic mixed resin are as follows:

Notched Izod impact strength 5.8

(kg.cm/cm ² , at 20 ⁰ C)

Macrographic transparency transparent and

slightly yellowish

_{Total light transmission} in $> or Ί

at 6 mm thickness ^D ''

Haze in fo at 6 mm thickness 7.3

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Claims (8)

2044887 claims 1. Thermoplastic resin made from 5 to 40 percent by weight of a composition (A), based on the mixed resin, the composition (A) being essentially composed of 60 to 90 percent by weight of at least one "acrylic acid ester, 40 to 10 percent by weight of acrylonitrile and / or styrene with 0.01 to 20 percent by weight of a diacetone-acrylamide compound and 5 to 0 percent by weight of a polymerizable crosslinking agent, based on the monomers, 5 to 120 percent by weight of a composition ("^), based on on the composition (A), the composition (B) consisting essentially of 40 to 100 percent by weight of methyl methacrylate and 60 to 0 percent by weight of at least one acrylic acid ester with 0.01 to 20 percent by weight of a diacetone-acrylamide compound bond, "based on the monomers, exists and - ■ · '■ · ■ the remainder being a composition (C) consisting essentially of 80 up to 100 percent by weight of methyl methacrylate and 20 to 0 percent by weight of at least one acrylic acid ester. 2. Process for the production of the thermoplastic mixed resin, characterized by (l) gradually polymerizing a mixture of monomers accordingly the composition (A), a monomer mixture corresponding to the composition (B) and a monomer mixture according to the composition (C) in any order and heating the polymer mixture obtained in the presence of an organic initiator which generates free radicals, 109819/2027 2,867 (2) gradually polymerizing a mixture of monomers accordingly the composition (A) and a monomer mixture corresponding to the composition (B) in any order, The solid polymer obtained is heated in the presence of an organic initiator which generates free radicals and mixing the polymer obtained with a copolymer, that by polymerizing a monomer mixture accordingly of the composition (C) has been obtained, and heating the polymer obtained in the presence of an organic radical supplying initiator or | (3) gradually polymerizing a mixture of monomers accordingly the composition (A) and a monomer mixture corresponding to the composition (B) in any order, mixing the solid polymer obtained with one Polymer obtained by polymerizing a monomer mixture according to the composition (C), and The resulting polymer mixture is heated in the presence of an organic initiator which produces free radicals. 3. The method according to claim 2, characterized in that the J polymerization by an emulsion polymerization process is carried out. 4. The method according to claim 2, characterized in that the Polymerization by a suspension polymerization process is carried out. 109819/2027 5. The method according to claim 2, characterized in that the diacetone-acrylamide compound used is diacetone-acrylamide v / ird. 6. The method according to claim 2, characterized in that the diacetone-acrylamide compound used is diacetone-methacrylamide will. 7. The method according to claim 2, characterized in that as crosslinking agents diol esters of unsaturated acids, unsaturated alcohol esters of unsaturated acids, diviny compounds or polymers of Diviny! compounds can be used. 8. The method according to claim 2, characterized in that the heating at a temperature of 90 to 130 C during 5 minutes to 8 hours in the presence of an organic, radical-generating initiator carried out ',' ■ - '' '- · · 109819/2027