DE1964913A1 - High impact resin - Google Patents

Description

According to the invention, weather-resistant, highly impact-resistant resins are obtained by polymerizing styrene or methyl methacrylate in the presence of a rubber-like mixed polymer of ethylene or α-olefins with a side chain of the formula CH _? = CHGOO- or

₂ = 0 (CH,) COO- and a polymer that contains butene, isobutylene, liquid paraffin or 1,2-polybutadiene.

The invention relates to a thermoplastic resin with extraordinary weather resistance and impact

0098U / 17 17

- 2 strength, especially at low temperatures.

Polystyrene and styrene-acrylonitrile mixed polymers are widely used as inexpensive thermoplastic resins. However, they have the disadvantage that their impact resistance is poor. To eliminate this disadvantage, these resins were mixed with a rubbery substance, polymerized or graft-polymerized, and these products are widely available in the market as high impact polystyrene or ABS resin (acrylonitrile butadiene styrene).

There have been several proposals for the manufacture of this high impact. _u en resins made. A widely used method is so-called "chain transfer type" graft polymerization which uses a peroxide series initiator such as a peroxide having a high capacity to hydrogenate in the polymerization of a styrene-containing monomer in the presence of a rubbery conjugated diene series polymer. In this package, the use of a rubbery conjugated diene series polymer is generally required in order to carry out the chain transfer type graft polymerization. At the same time, when this rubber-like substance is used, the high-impact resin contains an unsaturated double bond due to the presence of this rubber-like substance. Therefore

0O98U / 1717

there is a problem of deterioration due to ozone
and ultraviolet rays. In fact, this resin has almost no weather resistance. Therefore, in recent years, in order to improve the weatherability of high-impact resins of this type, the chewable substance has been modified using a saturated main chain. It was also found that by
Graft polymerization of a vinyl series monomer in
Presence of a rubbery substance suitable for the
Grafting is activated, a weather-resistant, highly impact-resistant resin is obtained by adding a double bond from one of the groups CH ₂ = CHCOO- or CH ₂ = C (CH,) COO- or mixtures thereof in the side chain of chewy copolymer from the group of Ethylene-vinyl ester copolymers or from α-01efin with 3 to 6 carbon atoms and vinyl ester.

In general, the impact resistance of such a resin gradually decreases with decreasing temperatures. However, when a vinyl monomer such as styrene or acrylonitrile is graft-polymerized using the above-mentioned graft-activated copolymer of ethylene or α-0] rfine alone, sometimes the impact strength p-solder lowers at a temperature below ^{0 ° C, and so does the graft polymer} tends to crack due to brittleness, although the impact resistance of the product at room temperature is excellent. Accordingly, it is an important goal of the present

009844/1717 BAD

Invention, a resin with excellent weather resistance whose impact resistance decreases only slightly as a result of a decrease in temperature «

Accordingly, the present invention relates to a weather-resistant, high-impact bath composition which has excellent impact resistance at low temperature and comprises a resin which is obtained by polymerizing a vinyl monomer with a Q-ehal-fy at least one of the monomers styrene or methyl methacrylate in the presence of a chewable material: or a-Olefinmischpolymers with a side-La-ir ^ i üle a CH ₂ = OHGOO group or a CH ₂ = 0 (CH ₅₎ includes OGO group or Migiehungen of these groups, and wenigstsns siror animal substances, a polymer with a SeIiGlΐ rc :: \ ^? ~ -r ^y :: ic - ^ - eas 50 φ butene lüid / or ieobutylene _s liquid paraffins im & 1 ^! -! ^ "^ .- ^ '''i ^ pdien, ge fig-at is .--

n & eli

η JL * Λ, ^ LA. * -m Kf · i '= - a. 'Vt. WiC in, * _β

iIi-iOi ---- = üiiigefüiarl · ΐ; ^ 2-άΐ, ^f X} mid setat sh

P *. .-. -, ■ - «CTf: = rs

BAO ORIGINAL

, a liquid paraffin (D) and 1,2-polybutadiene (B) and so wins a graft polymer.

Although ethylene, OH ₂ = OHp, is technically not a member of the α-olefin series, it still has a double bond at a terminal carbon atom and has the same function as an α-olefin in the present invention. Accordingly, in the description and claims, the term "α-olefin" is intended to include ethylene for the sake of brevity.

The preferred amount of the compounds (0), (D) and (S), the is added according to the invention, is 0.1 to 20 parts by weight. The amount from 1 to is particularly preferred

5 parts by weight per 100 parts by weight of the less from (A) and (D) holding polymers. When the amount added is / as 0.1 part by weight, the advantageous effect becomes the present Invention almost completely lost. On the other hand, when the amount added is more than 20 parts by weight, will difficult to add and the resin finally obtained becomes excessively white.

At least 50 wt $ butene and / or isobutylene-containing polymer, as it is meant here in the invention ₅ represents an amorphous homopolymer, such as butene or isobutylene, an amorphous copolymer of butene and / or isobutylene, or other olefins having no more than S Carbon atoms,

009844/17 * 7

especially at least one of the olefins from the group Ethylene, propylene, isoprene, butadiene, n-pentene-1, 3-methylbutene-1, n-hexene-1, 2,3-dimethylpentene-1, 2,4-dimethylpentene-1, 3,4-dimethylpentene-1, 4-methylpentene-1, isopentene-1, n-Octene-1 and Isoootene-1 and mixtures, at least one of these polymers,

Regarding the average molecular weights of these polymers becomes a number in the range from 200 to 5000 and preferably used in the range of 300 to 4,000.

The 1,2-polybutadiene, as it is mentioned here in the present invention, is polybutadiene, its main chain is polymerized at the 1,2 bond. Bs can also do something contain material polymerized at the 1,4 bond. fenn however the amount of the proportion of 1,4-bond 15 Grew .- # the weather resistance is reduced * Therefore, it is preferred that the amount of the proportion of 1,4- Bond less than about 15 wt%, preferably no more than 10 Grew .- ^.

An average molecular weight of such 1,2-polybutadiene in the range of 200 to 5,000, and preferably in the range of 300 to 4,000 is used. Material having an average molecular weight of less than 200 worsens appearance of a molded article made of this material, since fXi components tend to bloom from the molded article when the resin obtained is processed. · On the other hand

"■ 009844/1717"

SAD ORIGINAL

Solves an average molecular weight of more than 5000 unsatisfactory the object of the present invention and iat not preferred "»

The liquid paraffin, as set forth herein in the present invention, may be any liquid, commercially available paraffin and contain what is commonly referred to as a "process oil" of the Para ^ line series, which has a specific gravity of 0, 83 to 0.92 and a pour point below at least -5 ⁰ C, preferably below -1O ⁰ O, has.

The b © ± € © r tmiflying invention used- "can for example be produced according to a method you used at fez * l? © lymts> i @ & ti © s vos ABS ^ resin, isaeatli weiaa a © kaiitsehukartigs Srnbeteagj, Si © in eiasia loaomer with harsiMMosÄer capacity is resolved, polymsrisiart w ± rd _s -

im swei! Phaseia instead of ₅ because the ones formed from kü.i2.tsehuki, rtigaa Eubetans

favorable. sia & o ¥ ean dl © Poljaorisutioa at this point in time in the weseatlichea oiias rea imrehgeftiSifft wirä ₉ ^ ird the rubbery © substance

and- di <§ Hax'gphas © becomes the dis->

Maas® ο Wat <, räiessa ItostäwieH: feaaa keiae. Structure os ^ q & s ^^ 3. For the resin phase "is a · koatiaöierliche - W3 & 41 © Kamt © ehukpaas ©. a dispersed phase." GC- &is-; o @ afi «i _wl tets to achieve impact resistance ') * Therefore ^^ ■' ^ .sation of the monomer solution of the rubber

809844/171: 1; -

like substance is applied with stirring (this process is called prepolymerization). Especially at the initial stage of the polymerization, since the amount of the monomer solution of the rubbery substance is excessively large compared with the amount of the monomer solution of the resin component formed, the phase of the former is the continuous phase. However, as the polymerization proceeds, the amount of the latter phase becomes large. At this time, with the assistance of stirring, a phase inversion takes place, in which the phase of the monomer solution of the resin component becomes the continuous phase and the phase of the monomer solution of the rubber component becomes the dispersed phase. -If the prepolymer in which phase inversion took place-- " - then by suspension polymerization or

"Biodepolymerization is essentially polymerized without Sähres / · -up to " complete Polymsrisstioa "forms" -. "■" - ". ^; itself'a structure that. © is not finished? 11® Batst © hung of the - "

- Impact resistance viewed mrä »At fii © © ©! ³ ut ^ is & tuii ¹ becomes; di © Harskompoaente di © koatiaiaitrliöB.® Bias © -vm & öis "gohukkomponsnt- © dis diepergisrt®

As "grafted polymers according to the present invention, the"like; obea @ nnäta, t _P © EtoXtem w © rd © a ₀ ■ However, the invention ■ is not sp © si © ll ms £ this ©

-The ■ graft polymer lirz ,, wi © @ b ~ In the b © is _{9 is ®iaes s} in the ice styrene "and / or Methylmethycz'ylai; eatMlt, on 013a came

IAD ORIGINAL

Schuk-like α-olefin Miaohpolymei ·, in whose side chain at least one of the groups OH ₂ = OHCOO- and OHp = 0 (OH,) 000- has been introduced, is graft-polymerized Needless to say, the graft polymer resin may contain material in which a part of the monomer is not grafted onto the rubbery polymer, but that part of the yinyi monomer alone is polymerized to form a resin formed a mixture of a so-called graft polymer with a polymer of the vinyl monomer

In the present invention, there is the graft polymer resin essentially from 0.5 to 30 parts by weight of the rubber component and correspondingly from 99 * 5 to 70 parts by weight of the resin component, preferably from 2 to 20 parts by weight the rubber component and accordingly from 98 to 80 parts by weight the resin component, based on 100 parts by weight of the graft polymer.

The time at which (C), (D) or (E) according to the present Invention added can be before, during or after "completion the polymerization of the graft polymer, in the event that prepolymerization is carried out, can of course (C), (D) or (E) can be added at any point in time before, during or after the prepolymerization.

0 0 9844 /. 1-17 _ß AD

Y. ■. ■ - 10 - ■ - ..:. "-..-. '■■■.' · ■

If necessary, the time of addition can be divided into at least two parts, and (C), (D) or (B) can to be added at different times »If necessary or if desired, they can even be added continuously will. You can also use (C), (D) or (E) alone or with a Monomer, a plasticizer or a solvent can be added very thinly.

The rubbery α-olefin copolymer which is the basis for the rubbery ct -olefin copolymer which can be used according to the invention and has at least one CH ₂ = CHCOO- and / or CH ₂ = C (CH ₅ ) COO-G- introduced into the side chain. ruppe (A) is a copolymer from the group of ct-olefins, vinyl esters and vinyl alcohols. Regarding the content of the ct -olefin, the range of 65 to 95% by weight is preferred, and the range of 75 to 90% by weight is particularly preferred.

The corresponding ct-olefin is a ct-olefin with two to four carbon atoms, such as ethylene. Propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene-1 and 4-methylpentene-1. From the standpoint of practical use, ethylene is preferred. The corresponding vinyl esters are compounds of the general formula CH ₂ = CH-0-CX (where X is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 8 carbon atoms). Vinyl formate, fisjflacetats, vinyl propionate and vinyl fairaate can be mentioned in particular.

009844/1717

BATH ORIGINAL

Vinyl acetate is particularly preferred the proximity of 100 to 300 ⁰ O under an extremely high pressure of 100 to 3000 atmospheres. In order for this rubber-like mixed polymer to have good mechanical properties, it is preferred that the vinyl ester hardened is greater than all 35% by weight of the binding unit Main chains is, - '.-.'.

An a- @ löfia-? Lajlalk @ fe.®lffii @ ehpolymer or © in

can leie & t

la © for ti ©

Qit © ak © tt (3 a CHg -

fe © a © ieisa © t) l © gt @ llt ₃ öa.

only al® iüt (A) ..,

Olefia-Tiaylseter

= Via3Tl © st © ff =

from (I)
IREA (I) © rhsltea _s has old

- 12 - ■■■■ "- ■■ '..- ■■■

Acrylic acid (a), methacrylic acid (b), acid anhydrides thereof (o), acid chlorides of the same (d) or alkyl ethers of the same (β). In this case, if necessary, an acid catalyst such as hydrochloric acid, sulfuric acid or faratoluenesulfonic acid, or an alkaline one Catalyst, such as a methylate or ethylate of an alkali metals, such as ITatrium or potassium, are used. For example in the case of a combination of (I) with (e), it is

. possible to use sodium methylate as a catalyst to to directly effect a transesterification and thus a double bond to be introduced into the side chain of (I). In the case of a combination of (II) or (III) with (d) it is possible to introduce a double bond in the side chain of (II) or (III) by esterification without a catalyst. In the case of © © im © r combination of (II) or (III) with (a) or (b) it is when using paratoluenesulfonic acid as Catalyst possible to carry out an esterification in order to create a double bond in the side chain of (II) or (III)

r to introduce »

The amount of the double bond introduced into the side chain of the rubbery mixed polymer (A) is preferably from O ₉ 02 to 1.0 mmol based on the weight of the unit of (A) in ramm. Particularly preferably, the mixed polymer (A) contains O ₉ 04 to 0.6 mmol of the OH ₂ = CHCOQ- {J groups or CH ₂ = G (CH ^) GOO-ß groups, based on the. (Each unit of (A) in Sramm _o - · This is preferred by the stand puakt of

00 98 44/1717 BATHROOM o _RIGINAL .

ν impact strength of the polymer finally obtained. in the Case that such an amount is less than 0.02 mmol, the ratio of grafting of (B) becomes small and the impact resistance decreases. On the other hand, when the amount becomes larger than 1.0 mmol, the prepolymer sometimes gels during prepolymerization and formej; a three-dimensional Network structure so that it becomes difficult to phase reversal to reach.

To determine the amount of double bond> which is introduced into the side chain in the present invention, one can after complete hydrolysis of a kauts@hukaifci.gen α-olefin mixed polymer, in the side chain of which a double bond has been introduced, to acrylic acid or methacrylic acid to isolate, the normal method of adding bromine or use a standard chromatographic method.

The monomer used as the starting material in the present Invention can be used is a vinyl monomer containing styrene and / or methyl methacrylate, either another vinyl monomer that interacts with styrene and / or methyl methacrylate Is copolymerizable, such as acrylic acid alkyl ester (the alkyl group having 1 to 9 carbon atoms), such as for example acrylonitrile, methacrylonitrile, methyl acrylate, Ethyl acrylate and butyl acrylate, as well as methacrylic acid alkylesters (the alkyl group with two to aoht carbon atoms), such as ethyl methacrylate and butyl methacrylate, or a so-called

named styrene derivative such as α-methylstyrene and paramethylstyrene is also compatible.

The amount of styrene and / or methyl methacrylate used in the vinyl monomer is at least 50% by weight. When the amount is less than 50 wt. -Φ, occur despite the use of monomers ITachteile such as reduced moldability, and sometimes a molding is impossible. Also, the resulting polymer tends to be soft, its hardness decreases, its weight changes under the influence of heat, and sometimes it loses its thermoplasticity.

It is particularly preferred to use one monomer or a mixture of monomers to use that of (a) methyl methacrylate, (b) a mixture of styrene and acrylonitrile, (c) a mixture of Styrene, acrylonitrile and methyl methacrylate, (d) a mixture of styrene and aeryl methacrylate or (e) a mixture of methyl methacrylate and acrylonitrile, which is the content of each used in the invention Monomers can be in the range of the following formula »

χ + y + ζ = 100 (weight percent) 25 pounds 3.5 y + ζ = 150 0 Ä χ = 100 -25 / 3,5,0 * y »15O / 3» 5, OSz «

where x, y and a are the contents aa styrene? Acrylonitrile or

As PolymerisationsinftllÄr ^ beZm ^ olymeritiersa ämm ^ ⁰ ORIGINAL

Vinyl monomer in the presence of the rubbery "α-olefin raw polymer" can any known oil-soluble «Badikalpolymerieatiönskatalyaator, like an Az ο compound, for example azobisisobutyronitrile and azobiacyelohexanenitril, or a peroxide such as Bessoyl peroxide and Lauryl peroxide, be used. If necessary, thermal polymerization can be carried out in the absence of a catalyst will.

As mentioned above, in the present invention For example, initially a TFo rpolymeris ation carried out and after the phase reversal has taken place "i && t, will then be in a state that is essentially free of Movement is »a® suspension polymerization, or a Blookpolymerieation carried out., The temperature of the Prepolymerization and suspension polymerization or The block polymerisation depends on the properties of the vinyl monomer used and the type of initiator used depends. It's difficult to get the optimal temperatures Generalize esa? doek are generally temperatures ranging from 30 to. 250 ° C -applied.

As suspension stabilizers, which "in the suspension-- ' Polymerization according to the present invention can be used, normal anorgamiscke suspending agents, such as barium sulfate and calcium phosphate ,, and.normal organic Suspending agents such as polyvinyl alcohol., "- poly aorylate and Polyacrylamide.

. ÖAD ORIGINAL

00984Λ / 1717

It is also possible to add to the resin composition according to present invention various stabilizers such as phenol series, amine series, phosphite series stabilizers or the organometallic series, to be added to prevent deterioration

The impact strength at a temperature below 0 C of material that has a low impact resistance at temperatures * has temperatures below 0 C, according to the procedure of the present invention can be substantially improved. The reason for this is not clear. However, it is believed that each of substances (C), (D) and (E) have affinity to the rubber-type mixed polymer (A) has these Substances act like a plasticizer on (A) and maintain its softness even at low temperatures.

Since the resin composition according to the present invention has excellent weather resistance and impact resistance at room temperature and low temperature, - it can be used outdoors all year round can be used in areas where conventional Resins were previously unsuitable because of the harsh conditions. The usability of the resins has thus been considerably broadened according to the invention. The following examples serve the further explanation of the invention.

■ Ο09

example 1

An ethylene-vinyl acetate copolymer containing 19% by weight of vinyl acetate and methyl methacrylate was subjected to transesterification in toluene using sodium methylate as a catalyst in order to produce an ethylene-vinyl acetate copolymer in whose side chain 0.136 mmol / g CH ₂ = C (CH_ ) COO group introduced 1st. (a).

Thereafter, in a 1 liter flask equipped with a Dimroth condenser, a thermometer, a nitrogen inlet and a stirrer, kO g of the compound (a) and 5 S polybutene having an average molecular weight of 470 (such polybutene is a commercial mixture, which consists mainly of a polymer of a butene fraction which is mainly isobutylene) dissolved at 75 ° C. in a monomer mixture which consisted of 350 g of styrene and 110 g of acrylonitrile. After the compounds had dissolved uniformly, 0.05 g of azobisisobutyronitrile and 0.25 g of tert-dodecyl mercaptan were added and dissolved therein. At the same time, while the temperature was kept at 75 ° C., the speed of the stirrer was set to 250 revolutions per minute in order to initiate the prepolymerization stage. After about 3.5 hours, when the total solid component content of the polymerization system became $ 18.6, phase inversion occurred and the polymerization system was cooled with ice water to stop the polymerization. When the temperature returned to room temperature, 1.7 g of azobisisobutyronitrile became. added to the prepolymer syrup obtained and

: G0 9844/17 1 7

moderately dissolved in it.

On the other hand, in a 2 liter flask with a Dimroth condenser, a thermometer, a nitrogen inlet and a stirrer, one liter of an aqueous solution containing 0.05 $ of a methyl methacrylate-acrylamide copolymer (Weight ratio 20:80), whose pH with Sodium dihydrogen phosphate and hydrochloric acid (an aqueous Phase for suspension polymerization) was set to 6, and for this purpose, the prepolymer syrup was with Azobisisotbutyronitrile dissolved therein was added, and the rate the stirrer was set at 300 revolutions per minute set to initiate suspension polymerization. The temperature of the suspension polymerization was increased to 70 G held for four hours, increased to <? 0 C over 30 minutes and then kept at 90 ° C. for three hours to complete the polymerization to complete. After filtration, washing and drying of the Suspension polymer, it was molded by injection molding, and the physical properties of the resin obtained were examined. They are summarized in Table X. The resin had noticeably high impact strengths at low ones Temperatures.

Table I.

Physical properties of that obtained according to Example 1

Harzest

009 844/1717 ORiGIWAL INSPECTED

Impact strength (kg · en / en notch) Yield strength Breaking strength Elongation

(k / »2) (kg / c.4 (J)

23 ° C * 0 ° C * -10 ° C * -20 O C * 520 370 63 12.1 7.1 6.0 5. k

* Means the measuring temperatures. The measuring temperatures of the yield point, the
The breaking strength and elongation were all 23 C (etc.).

C £> CO

A test piece that can be put under roughly the same polymerization conditions was irradiated with ultraviolet rays from a weatherometer (irradiation conditions correspond to a rainfall of 18 minutes / 120 minutes, the temperature of a black plate of 65 C and an internal temperature of 43 C). After 300 β hours of irradiation the ratio of retained elongation at break to original elongation at break was $ 79, which is high. on the other hand was in the case of a commercially available ABS resin whose rubber component was a butadiene polymer after 100 hours Irradiation the corresponding ratio $ 19 »that is quite small is. In addition, the ABS resin showed a decomposition phenomenon such as cracks due to brittleness, and it was concluded that that the polymer in the present invention has a had much better resistance to weathering.

Comparative example 1

A 2 liter flask fitted with a Dimroth condenser, a Thermometer, a nitrogen inlet and a stirrer was equipped, was charged with 88 g of the ethylene-vinyl acetate copolymer, in the side chain of which a double bond was introduced was (a) as shown in Example 1. For this were 769 g of styrene and 242 g of acrylonitrile were added and after Method of example 1 resolved. When they were evenly dissolved, there were 0.11 g of azobisisobutyronitrile and 0.55 g tert-Dodecyl mercaptan added and dissolved therein. At the same time, a prepolymerization was carried out using the method of Example 1 initiated. After about 3 hours I turned the hare

. . .. 00 98 44/171 7

instead, and the fixed component salary became 18.9 ^. The polymerization The system was cooled with ice water to stop the polymerization. To 500 g of the prepolymer syrup obtained (b) Ij.7 'g of azobisisobutyronitrile were added and dissolved therein, and as in Example 1 followed by a Suspension polymerization and then the post-polymerization treatment. When the resulting suspension polymer deformed by injection molding and the physical properties of the obtained resin were determined the results listed in Table II:

0 0 9844/1 7 1 7 OBlGJNALINSPECTED

Table II Physical properties of the resin obtained in Comparative Example 1

a "impact strength (kg · cm / cm notch) yield strength breaking strength elongation C (kg / cm ² ) (kg / cm ² ) (%)

23 ° C 0 ° C -10 ° C -20 ° C
o 9-9 k.6 2.4 2.1 330 380 57

00 ■ "■ '■ ■.' ■■■■■■■. ■ · ■

S .3?

CD

cn (JD CO

As a result, it can be found that, in comparison with the resin obtained in Example 1, the impact strengths of the resin in particular were significantly inferior at lower temperatures. '- - - "■

Example 2

To 500 g of the prepolymer syrup (b) obtained in Comparative Example 1, 10 g of polybutene with an average molecular weight of 10% and 1.7 g of azobieisobutyronitrile were added and dissolved therein. Suspension polymerization and then the post-polymerization treatment were then carried out by the method of Example 1. When the resulting suspension polymer was injection-molded and the physical properties of the resin obtained were then determined, the results shown in Table III were obtained.

_om mi INSPECTED 0Ö984.W1717

Table III

Physical properties of the resin obtained according to Example 2

Impact strength (kg · cm / cm notch) yield point breaking strength elongation

(kg / W) (kg / cm2) (£)

23 ° c 0 ° C. -10 ° C. -20 ° C 510 380 54 11.7 7th 1 6.0 5-2

30 Ω

Z. CO ■ o

CD

CC CO

From these results, it can be seen that in spite of the fact that the same prepolymer syrup as in the comparative example 1 was used, the impact strengths were noticeably better at lower temperatures, since polybutene was added had been.

Example 3

Example 1 was repeated ₈ except that 5 g of liquid paraffin having a specific gravity of 0.845 was used in place of 5 g of polybutene to obtain a suspension polymer. When this polymer was molded by an injection molding method and the physical properties of the resulting resin were examined, the results shown in Table IV were obtained.

OB (SNA MSPECTEO 009844/1717 i "..

O O CO OO

Table IV

Physical properties of the resin obtained in Example 3

Impact resistance (kg - cm / cm Score; Stretch limit
(kg / c »2) Breaking strength
(kg / cm ² ) strain 23 ° C 0 ° C -10 ° C -20 ° c 10.7 7.3 6.1 5. 0 II
530 480 59
j,

F-

CD

cn CD

CO

These results also showed that the impact resistance at low temperatures were much better than those in Comparative Example 1.

Example 4

Example 1 was repeated with the exception that 10 g of 1,2-polybutadiene with an average molecular weight of 1,000 instead of 5 g of polybutene was used to obtain a suspension polymer. Venn this polymer through a Injection molding was molded and the physical properties of the resin thus obtained were determined, was obtained the results compiled in Table V.

9 8 LL f. Π17 nwGmAL IHSPECTEO

: J Table V

"Physical properties of the resin obtained in Example h

O O to OO

Impact strength (kg ♦ cm / cm notch) yield point breaking strength elongation

(kg / cm ² ) (kg / cm ² ) (#)

23 ° C. 0 ° C. -10 ° C. -20 ° c j ■■ ■ ■ 530 380 62 12th . 1 5. 9 H. 9 4.2

CD cn

CO \ CO

-. ²⁹ "■ ..; ■ 196491

The above results also showed that the impact strengths were significantly better at low temperatures, for example in comparison with those of Comparative Example 1 *

Comparative example 2

A 10 liter reaction vessel was charged with a 1 kg ethylene-vinyl acetate copolymer containing about 13% by weight vinyl acetate, 3.5 kg styrene, and 0.5 kg methyl methacrylate, and the temperature was adjusted to 75 "C- Then, 30 ecm 1.67 η sodium methylate was added to the reaction system as an esterification catalyst to obtain a monomer solution of an ethylene-vinyl acetate copolymer in the side chain of which 0.089 mmol / g CH ₂ = C (CH) C00 group was introduced was (0).

Thereafter, in a 1 liter flask equipped with a Dimroth condenser, a thermometer, a nitrogen inlet and a stirrer, 250 g of Compound (c) was placed, and then 148 g of styrene, 102 g of acrylonitrile and 0.5 g of tert-dodecyl mercaptan zugese.tzt _f and the temperature 75 C wurde'auf required to obtain a uniform solution. When the substances were uniformly dissolved, a prepolymerization according to the method of Example 1 was initiated. About 3.5 hours later, phase inversion took place and the solids content became $ 19.3. The polymerization system would be cooled with the aid of ice water in order to stop the polymer-saturation reaction. 1.7 g of azobisisobutyronitrile were now added to the above

given
The prepolymer syrup obtained and dissolved therein, as in Example 1

and then suspension polymerization and post-polymerization treatment were carried out. Then, when the obtained suspension polymer was molded by injection molding and the physical properties of the resulting resin were determined, the results shown in Table VI were obtained and the impact strengths were observed to be Temperatures not exceeding
-20 C were low. *

009844 / 17V7

ep whether OO

-3

? ■ · ■■ '■' '

f / Table VI

.ζ >

Physical properties of the resin obtained in Comparative Example 2

Impact resistance (kg , cm / cm notch / Stretch limit
(kg / c.2) Break-proofii ikeit strain 23 ° C 0 ° C - * 0 ° C -30 ° C 10.6 5 0 3.1 2.4 340 52 '

■ CD CD CO

Example 5

Suspension polymerization was carried out under exactly the same conditions as in Comparative Example 2 to obtain a prepolymer syrup containing 19.6% of solid components. Thereafter, 2 _t 5 g of polybutene with an average molecular weight of 470, 2.5 g of liquid paraffin with a specific gravity of 0.883 and 1.7 g of azobisisobutyronitrile were added to this prepolymer syrup and dissolved therein. Then suspension polymerization was carried out according to the method of Example 1 . A post-polymerization treatment was then carried out. When the resulting suspension polymer was molded by injection molding and the physical properties of the resin thus obtained were determined, the results shown in Table VII were obtained.

^0D9fU " ¹⁷¹⁷

Table VII

Physical properties of the resin obtained according to Example 5

Impact strength (kg ~ cm / cm notch) yield point breaking strength elongation

(kg / cm ² ) (kg / cm ² )

23 ° C 0 ° C -20 O c -30 ° C. 510 350 58 10.8 7.7 7,

ι. ■ U I

- 3k -

1964 91

From these results, it is evident that were regardless of the fact that practically the same prepolymer syrup impact strength at low temperature was used as in Comparative Example 2 _t much better, since it has been worked by the method of the present invention.

Example 6

fc Pre-polymerization was carried out under exactly the same conditions as in Comparative Example 2 to obtain a prepolymer syrup with a solids content of 18.9%. 1.7 g of azobisisobutyronitrile were then added to this prepolymer syrup added and dissolved therein. Now the method of Example 1 was suspension polymerization and then a post-polymerization treatment carried out. The resulting suspension polymer and polybutene with an average Molecular weight of 1,260 were determined with the help of 160 ° C heated salts mixed and kneaded to make bows. Then these sheets were cut up and pelletized Pellets were dried and then injection molded. When the physical properties of the resin so obtained were determined, those shown in Table VIII were obtained Results.

009R44 / 1717

Table VIII

Physical properties of the resin obtained in B _e ispie'l 6

Impact strength (kg < cra / cra notch) yield point breaking strength elongation

'(kg / cm2) (kg / cm *) (i)

23 ° C 0 ° C -20 ° C -30 ° C

ρ ■■ '.' ■■ ',. '■. . ■ '

to 11.2 7.2 5.h hU 520 '350

og praise -I- b j ^.

From the results it can be seen that despite the fact that practically the same prepolymer syrup as in that Comparative Example 2 was used, the low temperature impact strengths were much better because of the method according to the invention had been applied.

Comparative example 3

An ethylene-vinyl acetate copolymer with a content of 25 $> vinyl acetate and methyl methacrylate was subjected to transesterification in toluene using sodium ethylate as a catalyst to obtain an ethylene-vinyl acetate copolymer in whose side chain a CH ₂ = C (CH_) COO group was introduced (d).

Subsequently, into a 2-liter flask similar as employed in Example 2, 70 g of the substance (d) ", where this was added 837 g of methyl methacrylate, 93 S methyl acrylate and 3 S n ~ dodecyl mercaptan was added and the temperature was raised to 70 C set to dissolve the substances. After they were apparently uniformly dissolved, 0.1 g of azobisisobutyronitrile was added and, while maintaining the temperature at 70 ° C., prepolymerization was initiated. About three hours after the start of the prepolymerization, when the solid content became 21 ^, the polymerization system was cooled with the aid of ice water to stop the polymerization. 400 g of the prepolymerization syrup (e) thus obtained became 1.6 g of azobisisobutyronitrile Then, according to the method of Example 1, a suspension polymerization and a poly-

7T7 ■

ÖA ORIGINAL

-f ο ti Λ f; -i ο

- 57 - ■. I if! ο

merization post-treatment carried out. The suspension polymer obtained was molded by injection molding, and if the
When the impact resistance of the resulting transparent resin was measured, the results shown in Table IX were obtained.

Table IX _:

Impact strengths of the resin obtained in Comparative Example 3

Measuring temperature 23 ° C 0 ° C -10 ° C -20 ° C Impact strength 6.1 3 * 2 2.6. 2.3 (kg cm / cm notch)

Example 7

To 400 g of the polymer syrup obtained in Comparative Example 3 1.6 g of azobisisobutyronitrile and 2 g of 1,2-polybutadiene were used an average molecular weight of 2,000 and 2 g of butene with an average molecular weight of 470 added and uniform solved in it. After that, Comparative Example 3

wLederholt. Know the impact strength of the trans-

c. -

parent resin was measured, the results in Table X were obtained listed results,

Table X

Impact strengths of the resin obtained according to Example 7

Measuring temperature 23 ° C 0 ° C -10 ° C -20 ° C

Impact strength 8.3 5.Λ 4.8 3.8 (kgcm / cm notch)

It can be seen from the result that, despite the fact that the prepolymer syrup was exactly the same as in Comparative Example 3f especially the impact strengths at low temperatures were significantly better using the method of the present invention,

Example 8

Using exactly the same method as in Comparative Example 1 1,100 g prepolymer syrup with a grade of $ 19 »2 solid components (f) produced. Thereafter, it became 5OO g of substance (f) 5 g of polyisobutylene with an average molecular weight of about 2,000 and 1.7 g of azobisisobutyronitrile added and dissolved therein. After that, the resulting Solution subjected to suspension polymerization by the method of Example 1. After the resulting suspension polymer is subjected to post-polymerization treatment the polymer was injection molded, and when the physical properties of the resulting resin were determined, the results summarized in Table XI Results.

Q 0 9 8 LL / 1 7 1 7

Table XI Physical properties of the resin obtained in Example 8

O CO 00

Impact strength (kg * cm / cm notch) yield point breaking strength elongation

C. 1 0 ° C -10 ° < -20 ° C. (kg / cm- ) (kg / cni2) (^ ₁ ) 23 ° 7 ·. 4th 5.6 C. 4.9 1-2. 530 480 42

CO

: _ 4o - ■. ■■■■; 1 at; 4οι 3

The above results show that, despite the fact that practically the same prepolymer syrup as used in Comparative Example 2, the impact resistance at lower Temperatui * was much higher "

Claims (1)

Claims ! .Witterungsbeständiges, hochschlagf estes resin jni.t good impact strength even at low T _e mperature, characterized in that it comprises a blend polymer containing by polymerization of at least one of the monomers styrene and methyl methacrylate Vlnylmonomers in the presence of a rubbery iX-Olefxnmischpolyniers with a Side chain which contains one of the groups CH ₂ = CHCOO-orler CH "= C (CH_) 'C.OÖ— or mixtures thereof, with at least 5% by weight of butene and isobutylene before, during or after the polymerization , liquid paraffin or 1,2-polybutadiene added xfc vJürden « 2. Resin according to claim 1, characterized gekennzeiclme'i; that the The rubbery copolymer is a copolymer of 5 to 35% by weight vinyl ester of 65 - ^f ) 5% by weight of olefin. "- ■ .....- ν 3 · Resin according to claim 2, characterized in that the rubber-like C'C.-olefin copolymer an Ä thy 1 en vinyl acetate mixed polymer with a content of 65 - 95 weight r> Ethylene is. H. The resin of claim 1 - 3, characterized in that consisting of at least 50 wt - $> igeni butene, isobutylene, FLÜS S IF * <; existing rrt paraffin or 1, 2-polybutadiene substance ü ~ PO ι parts by weight based on 100 parts by weight of the Üarnjf-'S. ; 00 9 8 U ^ / Ι 717 _ ^ ₂ _ ι au -i - <yes w 5. Resin according to claim T - k _t, characterized in that the average molecular weight of the polymer containing at least 5 ° by weight ^ butene and / or isobutylene is about 2OO to 5OOO. 6. Resin according to claim 1 - 5t, characterized in that the Amount of side chain group 0.02-1.0 mmol, based on the weight of the units of the rubbery olefin mixed polymer in g. 7 · Resin according to claims 1-6, characterized in that it Essentially from 0.5 - 30 parts by weight of the rubber-like component and correspondingly 70 - 99.5 parts by weight dirrch len derl / polymerization of the vinyl monomer obtained resin component consists. 8. Resin according to claim 1 - 7t, characterized in that the Vinyl monomer, a mixture of styrene and methyl methacrylate Acrylonitrile, a mixture of styrene, acrylonitrile and methyl methacrylate was a mixture of styrene and methyl methacrylate or a mixture of methyl methacrylate and acrylonitrile is where the percentage of each monomer satisfies the following formulas: χ + y + ζ = 100 25 < 3.5 y + z <150 0 < χ ^ 100 - 25 / 3.5, 0 <. y <150 / 3.5, 0 <ζ <100, wherein χ, y and ζ are the contents of styrene, acrylonitrile and * ^: - - '0098ΛΑ / 1717 ^ Λ! ¹ ί Ι -1 Methyl methacrylate »expressed in terms of weight. OO 9 R LL / 1 7th ι 7 BAD