DE1941018A1 - Highly impact-resistant monovinylaromatic polymer compositions containing block copolymers and processes for the production thereof - Google Patents

Description

Hoolischlagfeate monovinyl aromatic, block copolymers containing Polymorenraasaan as well as method for Hsratel-

The invention relates to the production of hoonsönlagfeater monofinylaröffiätisöiier styrenic polymers and relates especially high-impact polystyrene-like polynes, which have a high grlans, good transparency as well as other desirable physical properties.

The invention makes high-impact styrene seals Resin masses with a comparable rubber content

0Ö98ÖS / 1670

and a smaller rubber particle size, a larger one Impact resistance and a higher gloss as well as at the same time a better Idohtdurohläseigkeit than known hoohsohlagfeste s ty roi-like hats are made available.

They are highly impact-resistant masses according to the invention The conditions occurring during extrusion are less sensitive than previously known impact-resistant styrofoam-like masses, and they are also less sensitive to these known masses are better suited for injection molding and shaping and also measure better and require shorter molding cycles.

A method also falls within the scope of the invention Production of tough etyrene-like polymer he, during the Carrying out the polymerization, the Tellchon size of the rubber can be controlled in a simple manner "and the rubber is less sensitive to shear"

The sole-resistant polymer compound according to the invention consists of (A) 80-97 weight of a polymer of at least 60 weight of a monovinyl aromatic monomer in which the vinyl group is linked to the benzene ring, this monomer containing up to 10 carbon atoms and another monomer which can be copolymerized with the first-mentioned monomer, and (B) 3-20% by weight of a whiskey -making coat, the weight given being the sum of (A) + (S). The toughening agent consists of at least (0) 3% by weight, based on the sum of the weights of (A) + (B), of a blook copolymer of a monovinyl aromatic monomer and 1,5-butadiene _a monovinyl aromatic monomer corresponds to the formula

OO90O8 / 1S7O

where E _{1 is} hydrogen or methyl. The blook copolymer is characterized in that the weight of monovinylaromatic units varies between 30 and 45 and the weight of 1,3-butadiene units varies between 55 and 70. DaB ELook-oopolymers has an intrinsic viscosity of approximately 1.2-1.7 and preferably 1.3-1 »6 dl / g, determined in toluene at 25 ° C. The weight average molecular weight varies between 100,000 and 500,000, while the number average molecular weight varies between 60,000 and 300,000. 5-25 f> of the butadiene units have a 1,2-vinyl Xonfiguration. The block copolymer has a Mooney Viekositett HL · -1-4 at 100 ⁰ C. of 50 - 150 and preferably 70 - 150. They sohlagfesten polymer compositions can (S) 0-4 weight ^ (based on the weight of the 0th ) + (B)) of a chewy butadiene polymer as a rope of the toughening agent «. It is important that the eye-making smock is uniformly and intimately blended into component (A), preferably in the form of particles with durohsohnittliohen surface knives of about 0.5-3 ^ x

A process for the production of a sole-bearing, styrene-like polymdrenal lake also falls within the bans of the invention. This process consists in creating a polymerizable mixture of (A) 80 - 97 weight? » of polymerizable materials containing at least 60% by weight of a monoviny! aromatic monomer in which the vinyl group is linked to the benzene ring, the monomer having up to 10 carbon atoms, and another monomer copolymerizable with the monomer mentioned to be dispersed in (AX 3-20% by weight of a toughening agent (B), where Bioh the weight - $ - refers to the sum of (A) + (B) , and where the toughening agent consists of at least 3 Gewiohte-jC, based on the weight of (A) + (B) from (C) dem

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• - 4 -

Bloek-Oopolymeren described above consists of a vinylaroioatiechen monomer and 1 _P 3-butadiene and, optionally, of 0-4 Qewiohts-jG of a rubbery butadiene polymer (D), and (A) bu polymerize, the mixture of (A) * (B) is subjected to a shearing movement at least when the umeate of (A) in the polymer is between about 10 and 30 wt.

Monomers which can be copolymerized with monovinyl aromatic monomers are known. Get used to its, for example, acrylonitrile and methyl methaorylate. Mixtures of Monovinylaromatic monomers alone or in combination with a copolymerizable monomer can also be used with the gate part. For example, a mixture of styrene and α-methylstyrene can be used.

The blook-oopolyoere is made from a diolefin, ' such as butadiene, and an eonoviny! aromatic Monomers, such as styrene, by mixing Butadiene and styrene in an inert anhydrous liquid such as toluene, heptane or xylene in the desired proportions and by adding a small amount of Butyllithiue su the cold or cooled Solution, whereupon the monomer mixture is polymerized. In carrying out such an operation, a HLook-Pplymeres with an A-B-X configuration is obtained. A consists mainly of polybutadiene and B mainly made of polystyrene.

According to a preferred embodiment, the blook polymer is in the monomer or in a mixture of the Monomers and the polymer auiTgeitJet. For example, can one proceeds in such a way that a partially polymerized solution of the styrene monomer and rubber, if necessary

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OBiGfNAt. fNSPECTED

in hybrid with an inert diluent, such as benzene, ethylbenzene, toluene, xylene or ethyltoluene, is used, the monomer for the recovery a solid styrene polymer, which also contains the block copolymers in intimate admixture, is polymerized.

You hates according to the invention are suitable for production of cups, containers, linings for refrigerators as well for the production of other shaped or extruded objects, such as films or sheets, which can then be deformed, for example by Vacuum priming.

In carrying out the invention, it is particularly important that the Mooney number of the block copolymer is carefully observed. For example, exceeds logarithmic Viscosity number (inherent viscosity) of the block copolymer the value of 1.7 »then the gloss is noticeably reduced. On the other hand, if the viscosity of the rubber is below 1.2, the impact resistance drops sharply. Block copolymers containing greater than about 45% by weight of a copolymerized monovinyl aromatic monomer a noticeably reduced impact resistance. Will be more than 70 weight- ^ butadiene used in the blook copolymer, then the gloss is noticeably reduced. ,

The rubbery butadiene polymers which can be used consists advantageously of polybutadiene or an emulsion-polymerized styrene / butadiene Eautschuk, containing up to 30 $ styrene. Such polymers have a viscosity of ML-1-4 at 100 ⁰ C of ^{20-210 4} O Ss is two-dimensional, the chewy butadiene polymer and the bloc

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Mix copolymers before mixing in the vinyl-aaatlsohe ISWKSB ₉ that is to be reinforced, see below. In. Such a Vernishen is advantageously carried out according to the invention.

The following examples illustrate the invention. example 1

Its pure high-strength polystyrene masses are produced by dissolving a blook copolymer in styrene, which contains approximately 0 ₉ 15 eewiohts-9 (an α-methylstyrene dimer, 1 Qewiohte-Ji mineral oil and 6 Qeviohts-9 (ithylberusol, the weights being based on the total weight of the Hasse besiehen prepared you Hisohung- is polymerized with stirring in a "boiler until at a temperature of 100 ⁰ C at the beginning to 130 ⁰ G after completion of a tent range of about 3 hours Iftnsats of 25 -. 30 Jt has been reached · They temperature is then raised ansohlieesend over a period of 5 hours to 170 ° 0 to about 80 £ of the monomers have been converted into the polymer. It Beaktlonsmisohung is then under vacuum to a temperature of about 200 to about 240 ⁰ C under reduced Sruok is heated to remove residual monomers and ethylbenzene, the molten mixture is cooled, extruded and pounded into granules at is subsequently deformed. The test results determined using the deformed granules are summarized in Table I below.

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to g

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! 888888888 ICX M

^ «~ M« V ** IA <O fr- ID CR

049808/1670 ORIGINAL INSPECTED

Example 2

The procedure described in Example 1 is repeated using 6% by weight of acrylonitrile, 6% by weight of ethylbenzene, 1% by weight of mineral oil and the specified amount of block copolymer and styrene. The solution is polymerized to a conversion of approximately 18-28 # in a kettle while being guided. 11 # acrylonitrile, which contains 9 $> ethylbenzene, is added to the polymerization mass, whereupon the polymerization is continued with a temperature rise of 140 to 175 ° 0 until a conversion of about 80 pounds has been obtained. The reaction mixture is then freed of volatile components at a temperature of 200 - 240 * 8 with reduced bridging.Following this, the molten polymer is cooled, extruded and cut into granules, the granules are then shaped, whereupon the moldings are examined. The results are summarized in Table II. ,

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SEable II

jS block- ⁷ P ¹ - ¹ 'MIr-1-4 ^v - ^; S / B ^ 'M ^_6/4' Mj? 'Schmela- IZOD- DARI- Gloss Oopolymeres ^w "viscous! - Sehlag- Impact-

speed

* 7 0.8 * 7 1 7th 1 »3 7th 1.4 7th 1.4

25 30/70 69 42 7500 0.08 10 14

33 ^ 30/70 108 66 9900 0.14 10 10

70 30/70 161 99 6500 0.17 44 61

g 7 1.4 95 30/70 189 133 7800 0.15 17 52

«> 7 1.4 129 40/60 186 146 4500 0.20 25 35 *

oo % O

oo * comparative examples'

^ ^ ¹ ^ Intrinsic energy in dl / g in benzene at 25 ° 0

2 ^ ² ^ Mooney-ViBkoeität ML 1 + 4 at 100 ° 0 ο C3) _{styrolsButadlea-} . _{Yerlläliiaie}

Molecular weights χ 10 Molecular weights χ 10 ~ ⁵ Using a flaetometer at 22? ° C In ailcg

2.1 Bt waste on a 2.54 ran thick extruded film

$ Reflection from a 'flat surface' formed in a vacuum,

Similar results are obtained if an emulsion-polymerized styrene / butadiene rubber, which contains 50 parts by weight of styrene and 70 parts by weight of polybutadiene in an arbitrary distribution, is used instead of polybutadiene, and the blook copolymers of vinyl toluene (mixed isomers) and polymers 1,3-butadiene. Polymers produced according to the invention according to Examples 1 and 2, in which rubber is distributed, the waist size from approximately 1/2 to approximately 3 µm, have excellent shape and intrusion properties, glossy surfaces and tend to save significantly *, the transparency being determined in such a way that a shaped section of a thickness τοη approximately 3.2 im (1/8 inch) is laid over a page written or printed with with ink. The polymers are also very easy to extrude, with only slight curling.

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Claims (1)

- 11 -patent claims A mass of (A) 80-97 weight- ^ of a polymer of at least 60 weight- ^ of a monovinylaromatic monomer in which the vinyl group is linked to the benzene ring, this monomer containing up to 10 carbon atoms, and 0-40 weight- ^ of another monomer which is polymeric with the first-mentioned monomer, and (B) 3-20% by weight of a vision-making agent which is uniformly distributed in (A) in the form of small particles, the weight being given on the sum of (A) and (B), characterized in that the look-making agent consists of (O) 3 weight- ^, based on the weight of (A) + (B), of a blook-Oopolymer of 1, 3-butadiene and a monovinyl aromatic monomer of the formula in which H _{1 is} hydrogen or methyl, or contains the stated material in the specified amount, the amount by weight of monovinylaromatic units fluctuating between 30 and 45 and the amount by weight of 1,3-butadiene units between 53 and 70, the blook -Oopolymers has an intrinsic viscosity of about 1.2-1.7 dl / g, measured in toluene at 23 ° 0, has a weight average molecular weight of 100,000-500,000 and a number average molecular weight of 60,000-500,000 and has a Mooney viscosity ML-1-4 at 10O ⁰ O has from 50-150, and where 5-25 pounds of the butadiene units have a 1,2-vinyl configuration. 00980871670 2. Composition according to claim 1, characterized in that the toughening agent contains up to 4 Gewiohts- # of a chewable butadiene polymer »based on the weight of (A) + (B) ₉ . 3. Composition according to claim 1 or 2, characterized by » that (A) is a polystyrene or a copolymer of styrene and acrylonitrile. 4. Cash register according to one of claims 1 - 3, characterized in that the blook gopolymer has an intrinsic viscosity of 1.3-1.6 dl / g. 5. Hasse according to one of claims 1-4 »daduroh characterized in that the monovinylaromatlsohe monomers (B) from Is made of styrene. 6 · mass according to one of claims 1-5, characterized in that the particles of the toughening agent a have an average diameter of 0.5 - 3 u 7 · Composition according to one of claims 2-6, characterized in that the chewy-like butadiene polymer is made from Polybutadiene or a copolymer with an arbitrary distribution of butadiene and styrene, which is up to 30 Gewiohts-Jt Contains styrene. 8. Process for the preparation of a polymer with high Impact resistance using a polymerizable «!!. Mixture of (A) 80-97 weight-5 * polymerizable material, the at least 60 weight- ^ of a monorinylaromatic monomer in which the vinyl group is linked to the benzene ring, the monomer up to 10 carbon 009808/1670 contains atoms, and 0-40% by weight of another monomer copolymerizable with the monomers mentioned, where in (A) 3-20% by weight (B) of a toughening agent are dispersed, and where the percentage by weight is based on the sum of (A) and (B), characterized in that the toughening agent used is at least 3% by weight, based on the weight of (A) + (B), (G) of a blook copolymer of 1, 3-butadiene and a monoviny! Aromatic monomer of the formula HO = OH ₂ contain where B ^ is hydrogen or methyl, and where the weight of monoviny / aromatic units is 30 to 45 and the weight of 1,5-butadiene units is 55 to 70, the Bloek copolymer has an intrinsic viscosity of 1.2-1 , 7 dl / g, determined in toluene at 25 ° 0, has a weight average molecular weight of 100,000-500 and a number average molecular weight of 60,000 to 300,000 and a Mooney viscosity ML-1-4 at 100 ° 0 of about 50 - 150 has ₉ and where 5 - 25 # of the butadiene units have a 1 _f 2-7ynyl K © nfigurati © a, and (A) is polymerized while the mixture of (A) and (B) is subjected to at least during the time a shearing movement during which the conversion of (a) to the polymer 10 to 30 wt ^ ₀ 9 ο method moh claim 8 _B characterized in that in addition (S) up to 4 weight ^, based on the weight of (A) and (B), of a rubber-like butadiene 009808/1670 Polymers are used. 10. The method according to claim 8 or 9t, characterized in that the Xautsohuk component is dispersed in the form -von ItBiIoIiBn with an average Surohmesser of O ₁ Si to about 3 u . 11. The method according to any one of claims 8-10, characterized in that (A) consists of polystyrene or a copolymer of styrene and acrylonitrile. 12. The method according to any one of claims 8-11 »characterized in that the block copolymer has an Xntrinsic viscosity of 1.3-1 * 6 dl / g» 13 · The method according to any one of claims 8-12, characterized in that the monovinylaromatic honey from (B) is made of styrene. 14. The method according to any one of the claims 8-13, characterized in that the toughening agent! Polybutadiene or a copolymer with an arbitrary distribution Contains butadiene and styrene, which has a styrene content of up to 30% by weight. 009808/1670