DE1694668A1 - High impact polyvinyl chloride resin compositions and processes for their production - Google Patents

Description

Impact-resistant polyvinyl chloride resin compositions and methods for their

Manufacturing

The invention relates to resin compositions as the main component a polyvinyl chloride resin (hereinafter referred to as PVC resin), and which has an improved processability, a have excellent impact resistance and weather resistance, and a method of manufacturing these resin masses. The resin composition according to the invention is made of | 50 to 95 parts by weight of PVO resin and 5 to 50 parts by weight a resin made from an acrylate elastomer which is crosslinked with the aid of an organic peroxide and one mainly composed of Styrene, methyl methaorylate or vinyl chloride composed of polymers

PVC resins are cheap and have excellent chemical properties physical properties so that they are manufactured in large quantities and widely used in various fields will. However, PVC resins have the disadvantage that they

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Due to their brittleness, they have a low impact strength and are difficult to process. In recent times, extensive studies have been carried out on improving the impact strength and processability. PVC resins ^r Toggle found, as a result, various weights of these resins have been indicated with improved properties and methods of making.

As an effective method for improving the processability and the impact resistance of fVÖ * resins, a method is known in which PVG resins are mixed with natural or synthetic rubber or with a resin which is obtained by polymerizing at least one monomer in G-egen "" • Was obtained from natural or synthetic chewing schools:. was used, the monomer used being that which, when polymerized in the absence of rubber, is a hard one. : / and gives brittle resin, such as styrene, methyl methacrylate and / or acrylonitrile »Attempts were also made to use PVC resins. with practically all synthetic elastomers or with graft * · polymers made using these elastomers; were to be mixed (under ¹ IP graft polymers ¹¹ are next understood the polymers that are obtained by polymerizing: ^ ■ ' monomers in the presence of elastomers), *, - \: ΐ especially: suitable substances for mixing with : .PVe *: - ~; ·. y \ _: Resins are the so-called ABS resins that are obtained by polymerizing styrene and acrylonitrile in the presence of polybutadiene = · styrene-butadiene rubber. iypisöhe

00983S / 1773

for these substances are "Blendex" (manufacturer: Marbon. Chemical Division of "Borg-Warner Corp. o) and" Paralloid "(manufacturer: Rohm & Haas Co.). These substances are excellent agents for improving processability and Impact resistance of PVC resins, however, have the disadvantage that their thermal resistance and especially their weather resistance are poor, so if compositions of these improvers and PVC resins are used outdoors, they lose their mechanical properties, especially their impact resistance relatively short tents These difficulties-based-im.wesentlichen on the structure of the elastomeric polybutadiene or styrene-butadiene rubber, d _o h on the left in the main chain of the elastomer double bond -. "." Even if ... one uses stabilizers of the most varied types, - a significant improvement in weather resistance - cannot be expected «

On the other hand, resins obtained using saturated elastomers without a double bond in the main chain have excellent weather resistance, but most resins are poorly compatible with PVC resins. Accordingly, .iMas.sen,. That have. Mixing these resins with PVG resins resulted in a low impact resistance, poor - .. over -surface _: en ^.; ^ Ens.c. adhesion (gloss) and in general a low pe ^ st ^ ke -! .- ^ ;. It, “are also numerous improved; Tills known ,, ..the _; , lower.r, de ^ ter ^ dung. of acrylate; the. kind of. represent saturated elastomers,

0 0 9 6 3 5/1 773

were manufactured. However, the bulk are the 'PVC resins as well as resins made using acrylate elastomers prepared by the ordinary known methods are generally difficult to process when mixed together using a mixing roller and have poor surface properties (gloss) and low impact resistance "

Purpose of the invention .is to improve the impact resistance and processability of PVC resins during -Simultaneous' ■ many excellent characteristics such as excellent weather resistance u.dergl. to be maintained "

In particular, the invention aims to provide PVG resin compositions with excellent impact resistance, processability and weather resistance, as well as a method for Manufacture of these masses. ■ -

Taking into account the fact that acrylate elastomers have excellent weather resistance, the The inventors made extensive studies in order to use these elastomers to produce PVC resin compositions with an excellent To maintain impact strength, processability and weather resistance. As a result of these investigations was a process for the production of novel crosslinked Acrylate elastomers, it being found that a «let, which is made of a PVC resin and a resin which is a

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Crosslinked Acrylate ™ elastomer produced by this process and containing a polymer obtained by polymerizing a monomer with at least one substance from the group consisting of styrene, methyl methacrylate and vinyl chloride as the main component, is suitable for the desired purpose and has excellent impact resistance, processability and weather resistance possessed _f ,

In order to obtain a PVO resin race with excellent impact resistance, processability and weather resistance using an acrylate elastomer, it is absolutely necessary that the aorylate elastomer has been crosslinked in the form of an aqueous dispersed satellite by the method according to the invention. Although the acrylate Blaatomere to be * - known methods was crosslinked using, for example, a polyfunctional vinyl compound such as ethyl englykoldimeth "· acrylate or Biviny used benzene _t see the leaves

■ '- i

do not improve the mass. Under the ^

In the present case, an aorylate "polymer" is understood to mean at least one alkyl arylate; with an alkyl group with 1 to 10 Q * A * teomen or contains, which dureh ypolymeris a% in one eye 60 ^ ewiohtateilt »or more at least one alkylaorylata with an alkyl group from t to 10 'GMtfcomen and 40 ^ twiahtfilien or less at least tine monomers from the group of AcsryJnitril | Acrylgöurei Iethaorylaäure _t styrene _f Alkylmethaorylat en with alkyl groups with 1 "to 10 C-atoms and. Vinyl-

chloride was obtained (under ".Polymers" should also be "mixed polymers" be understood.).

The masses according to the invention are produced as follows:

First are working methods for making networked Acrylate elastomers specified *

Dissolve 0.7 Ms 5 parts by weight, preferably 1> t is 3 parts by weight of an organic peroxide with bucket Zersetzungstempe- 'rätur of 55 ⁰ C or above at a temperature of 30 ⁰ O or less in 100 parts of a monomer consisting of at least an alkyl acrylate with C ^ -C-alkyl groups or from a monomer mixture that contains 60 parts by weight or more of at least one of these alkyl acrylates and 40 parts by weight or less of at least one monomer from the group consisting of acrylonitrile, acrylic acid, methacrylic acid, styrene, alkyl methacrylates with Gj ^ ö ^ Q-alkyl groups and vinyl chloride. The resulting solution is exposed to deionized water in which an emulsifier has been dissolved beforehand, and the atmosphere of the system is replaced by nitrogen preferably at a temperature which is 20 ^° C. or more below the decomposition temperature. After the polymerization of the monomer has practically ended, the latex is heated with stirring to a temperature above the decomposition rate.

ooms / ma .. ",

temperature of the organic peroxide, a crosslinked elastomer latex being obtained. Understood by decomposition temperature one a temperature "at which the peroxide in 10 hours to Half is decomposed.

The organic peroxide used for crosslinking should be as follows Conditions are sufficient!

(i) Its decomposition temperature should be 55 · 0 or

lie above?
(ii) It should be soluble in the acrylate monomer, but soluble in water

hardly soluble (A peroxide dissolved in water at 30 ⁰ C to 15 $> or more is not preferable.)! (iii) it should be difficult to achieve rapid, induced decomposition under the action of the growing polymeric radicals.

Organic Peroyde "which meet the conditions given above," are "for example lauroyl peroxide, benzoyl peroxide, Octanoyl peroxide, cyelohexanone peroxide, p-chlorobenzoyl peroxide, Dicumyl peroxide, di-t-butyl peroxide, butyl perbenzoate, t-butyl peracite and t-butyl peroctoate. As emulsifiers you can use ordinary Emulsifier; are used *, · '

The one for the .Emulsiön'spo ^ mBrrsation of. Redox initiator used in monomers must _; way3serl: b * sl ^: i- s; a: and: should in the aqueous phase rl @ s - MonoiEer- ^ fease; r «-Gemi: S: ChjBs _; des Polymeri sat i ons ay st ems

00983S / 1773.

but hardly soluble in acrylate monomers. This is especially true for the lall when one uses a compound as a reducing agent of a redox couple is used, and it is not preferable to use a compound dissolved in the monomer which contains the Decomposition of the organic dissolved in the monomer phase Peroxides favors. Preferred redox initiators are, for example, potassium persulfate-sodium thiosulfate, potassium persulfate-sodium bisulfite, Ammonium persulphate-sodium sulphite and hydrogen peroxide-perro salts =

The crosslinking density of the elastomer can be determined by suitable Selection of the type and amount of organic peroxide, the baking temperature, the heating time or the stirring conditions During the crosslinking reaction can be varied as desired «Furthermore, one can avoid the cleavage of the polymer to prevent during the crosslinking reaction and increase the efficiency to increase the networking or to the networking Shorten the required time, use substances which promote the decomposition of the organic peroxide or which can be used after the completion of the polymerization of the acrylate monomer also add other connections. These compounds are, for example, amines, quinones, quinoximes, Allyl compounds and diallyl compounds. Became an organic one Peroxide with a decomposition temperature of 100 C or more is used, so the crosslinking of the elastomer can take place Pressure in an autoclave or in the presence of fresh, decomposing Substances are carried out.

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The elastomer latex obtained in this way is not only mechanically stable, but also during transport or storage.

Crosslinked elastomers, which are used for the production of the masses according to of the invention can only be obtained if the combinations of organic peroxides and redox initiators given above are used «If one uses no such combinations, difficulties arise during the polymerization and only elastomers are obtained, the registers with poorer physical properties result.

An elastomer crosslinked to a certain extent can also be obtained by a process in which a solution of an organic peroxide in an organic solvent is added to a polyacrylate latex produced in a manner known per se, whereupon the mixture is heated the organic peroxide does not always penetrate into the interior of the blastomer parts, whereby an unevenly crosslinked elastomer is obtained in which only the surfaces of the elastomer particles are crosslinked. Furthermore, the latex is not the organic one used to dissolve or dilute the organic peroxide ! solvent unstable, but you also have to remove the organic solvent, which complicates the work steps and causes economic disadvantages * " ^v '" ^r ~ "

The mass according to the invention is composed of (A) a resin, obtained using the above crosslinked elastomer, and (B) a PYG resin. The resin (A) contains resins of (1) mixed type, (2) graft type and (3) graft mixed type, each of which is made in the following ways:

The mixed resin (1) is divided by mixing I5 his 60 Gerichtsk crosslinked elastomer (a) with 40 His 85 parts by ^weight: a polymer (h) prepared by polymerizing at least one monomer such as styrene, methyl methacrylate or vinyl chloride, or a Monomerengemisohes of 60 Parts by weight or more of at least one monomer of the type specified above and 40 parts by weight or less of at least one monomer from the group of acrylonitrile, C ^ -Methylstyröl, methacrylic acid, acrylic acid and AlAylacrylaten with C-Cj q-alkyl groups was obtained «Usually (a) and (b) mixed with each other in the form of latices, whereupon the mixture is coagulated, washed with water and dried, whereby the mixed resin (1) is obtained «

The graft resin (2) is polished by polishing from 40 to 85 parts parts by weight of the monomers that make up the above polymers (b) form, in the presence of 15 to 60 parts by weight of the crosslinked elastomer (a). manufactured. In this EaIl Small amounts of an emulsifier and / or an agent to regulate the degree of polymerization can be added. as

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For the polymerization initiator, a common initiator is used.

The graft-mix type resin (3) is prepared by mixing the polymer (Id) with a graft polymer (2 ¹ ) obtained by polymerizing the monomers constituting the polymer (Td) "in the presence of the crosslinked elastomer (a ) Usually, (2 ^r ) and (Id) are mixed with each other in the form of latices, and the mixture is coagulated, washed with water and dried to obtain the graft-mix type resin (3) however, it is also permissible ^{to mix (2 f} ) and (b) with each other in Torrn of powders. In this case, too, the content of crosslinked elastomer should be 15 to 60 parts by weight per 100 parts by weight of the graft-mixed resin (3) »

In each case (1), (2) and (3) it is necessary that the Crosslinked elastomer content is 15 to 60 percent by weight. If the elastomer content is less than 15 percent by weight, | then, when mixed with PVC resin, the resin (A) gives one Cash register that is easy to process, but has a low impact resistance. On the other hand, the content of elastomers is more than 60% by weight, the resin (A) provides when mixed with PVC resin a compound with poorer strength and poorer surface properties (gloss). Particularly an elastomer content of 30 to 10% by weight is preferred.

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The PVC resin (B), which is another component of the composition according to the invention, contains? "(4) polyvinyl chloride, (5) mixed polymers with 70 parts by weight or more vinyl chloride and 30 parts by weight or less of at least one monomer from the group vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid, methacrylic acid, alk-ylacrylafe with C ^ -O ^ Q- Alkyl groups, alkyl methaerylaie with CjC ^ -alkyl groups and ethylene, as well as _fc (6) chlorinated PVC resins, which were obtained by chlorinating (4) and (5) in a manner known per se. Preferred chlorinated PVC resins are those with 62 " up to 71 ° chlorine »The PVC resins used here are produced in a manner known per se by emulsion polymerisation, suspension polymerisation or polymerisation in bulk.

The resins (A) and (B) are mixed together by means of a known mixing means such as mixing rolls, Banbury mixer or plastograph In some cases, they can be mixed in a ψ mixing extruder or can be premixed prior to the actual mixing in a ribbon blender or a Hens Helmi shear. Furthermore, the resins (A) and (B) can be mixed with one another in the form of latices. If necessary, the mixing can take place in the presence of known stabilizers, plasticizers, lubricants, pigments or fillers.

The resins (A) and (B) are compatible with each other in all proportions, but the amount of the resin (A) in the composition is usually 5 to 50% by weight, preferably 10 to 30% by weight . is

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the amount of the resin (A) less than 5% by weight, so improved the impact resistance and the workability of the mass hardly differ? if the amount of the resin (A.) is more than 50% by weight, thus the composition has poor tensile strength, poor hardness and poor surface properties

The invention is explained in more detail below with the aid of the examples, but the examples are by no means intended to illustrate the invention ". In the examples, all parts refer to and percentages based on weight.

"Examples 1 - 3 Synthesis of crosslinked acrylic elastomer (E-1)

n-butyl acrylate 90 parts

i / iethyl methacrylate 10 "

Benzoyl peroxide 2.0 "

Potassium persulfate 0.3 "

Sodium bisulfite 0.1 "

Sodium Lauryl Sulphate 2.0 "

Deionized water 200 "

According to the instructions given above, the benzoyl peroxide was first ^{dissolved in the monomer mixture at 20 °} C. The solution was added to an aqueous solution which contained the initiator and the emulsifier and which were poured into a reaction vessel

became. After purging the reaction vessel with nitrogen, the mixture was polymerized for ^{seven hours at 35 0} O (degree of conversion 92 f °) The latex formed was heated to 90 C and stirred for a further eight hours, a latex of a crosslinked elastomer being obtained « A part of the elastomer latex thus obtained was coagulated and dried. whereupon the gel content and swelling index using. of methyl ethyl ketone were determined as the solvent. Of the ; Gel content was 90 ^ and the swelling index was 8.6. The ... gel content and the swelling index are understood to mean the values that are calculated using the following equations:

Gel content = S ^ χ 100

W swelling index =

wherein W is the total swollen amount (g) g of a dry sample 0.3 was immersed for 48 hours at 30 ⁰ C in 100 ml Methylähtylketon, and Wo represents the dry weight of the immersed sample.

Production of the resin (A) t ■

(i) Preparation of the mixed type polymer (1) :.

Styrene 70 Parts ■ - ■ .. · ^; -% ■ -:. Acrylonitrile •1 Potassium persulfate O, 1 '·- n-lauryl mercaptan O, 2 ··· 0 0 9 8 3 5/1773 Sodium lauryl sulfate 1, 0 » Deionized water 200 Il

A mixture having the above composition was five hours .for 60 ⁰ C polymerized (degree of conversion 96 f °). 65 parts (based on the pesticide content) of the polymers formed and 35 parts (based on the pesticide content) of the crosslinked elastomer (E-1) were mixed together in the form of latices. The mixture was calcium chloride solution to coagulate by addition of an aqueous, washed with water and then dried to obtain a white polymer was obtained i.

(ii) Preparation of the graft type polymer (2) i

Elastomer (E-1) 35 parts (based on the

Pests)

Styrene 45.5 "

Acrylonitrile. 19.5 "

Potassium persulfate 0.1 «

n · liauryl mercaptan 0.1 "

Deionized water 200 ""

A mixture having the above composition was reacted for five hours at 60 ⁰ C (the degree of conversion 97 f °). The obtained latex was coagulated by adding an aqueous calcium chloride solution, washed with water and then dried to obtain a powdery polymer (GI).

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(iii) Preparation of the graft-mix type polymer (3) i

Elastomer (E-1) 50 parts (based on

Solids)

Styrene 35 If Acrylonitrile 15th It Potassium persulfate O, 1 "

Deionized water 200 "

A mixture with the above composition was ^{reacted at 60 °} C. for five hours. The obtained latex was mixed with the latex of the mixed type polymer (1) so that the content of crosslinked! Elastomer made up 35 i ° of the total amount of the mixture. Then, the mixture was coagulated by adding an aqueous calcium chloride solution, washed with water, and then dried to obtain a white powdery polymer.

In each case 20 parts of the polymer of the mixed type (1) obtained in this way, of the graft polymer (2) and of the graft copolymer (3) were mixed individually at 175 ° C. for 10 minutes on a mixing roller with 80 parts of "Geon IO3-EP" (PVC, manufacturer Nippon Geon Co.f average degree of polymerization 1050), 1.5 parts of barium stearate and 1 part of dibutyltin maleate mixed. Then, the mixtures were molded for 7 minutes at I85 ^'0 C at a pressure of 200 kg / cm by pressing, after which the values given in Table I were determined.

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TaTa rush 1

ι ''"
\ ^^ Bar 7, A-
P- ; T 3iIiG Ii 3C ^ e--.
2'ig snscr-, _; ■ ΐen ^^. example 1
(Mixed
polymer) Example 2
(Propf-
polymer) Example 3
(Graft Mix
polymer) ! Impact resistance +1
; (kg - cm / cm ^) 16.3 27.6 24.2 Schraelz index +2
(g / 10 min.) 8.6 7.2 7.6 Rockwell hardness (R) 108 108 106 Heat deformed temperature * -
rature +3 ( ⁰ O ' 82 85 83 Tensile strength +4
(kg / cm2) 430 410 400

+1 s Oha-rpy impact strength (sample 10 mm 90 mm χ 3 mm,
Depth of the V-notch 1mm)

+2: Flow rate per 10 min. / ^{When using a melt index device at 200 0} C and 30 kg / cm ^ (opening diameter 2.005 mm, length 8.00 mm)

+3 »Measured according to ASTM D-648-56 +4: Measured according to ASTM D-638-58T

As T _a ble I shows one of the Pfrojjfpolymeren obtained using the mixed polymers, a composition having good flowability, when using a composition with high impact strength and

00983S / 1773

when using the graft mixed polymer a compound with properties, which lie between those of the other two masses » So it can be produced relatively easily with different properties,

Examples 4-10

For the production of crosslinked acrylate elastomers, a Monomer mixture of 88 parts of n-butyl acrylate and 12 parts Methyl methacrylate used? the amount of benzoyl peroxide added was varied as indicated in Table II, the elastomers given in Table II were obtained. In the presence of 40 parts of each of these elastomers, a Monomer mixture of 42 parts of styrene and 18 parts of acrylonitrile polymerized to obtain the resin (A). The other conditions were the same as when the Graft polymers according to Example 2.

The impact strength values of the masses with 20 parts of each Resins (A) obtained as above and 80 parts of Geon-IO3-EP (PVOj manufacturer Nippon Geon Go.) Are given in Table II.

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Table II

- Added
lot 2 0.3. Properties of the
Elastomers - Impact resistant
ability .. ₂ Benzoyl
peroxide (? ο) 3 0.5 Gel content swelling * -
(fo) index - (kg-cm / cm ^) Comparative example Diel O
1 4th 0.7 O 70 9.7 Il 5 1.0 5 36 10.2 Il 6th 1.5 20th 18th 11.3 example 7th 2.0 60 10.2. 15.2 Il 8th 3.0 77 7.8 19.2 Il 9 4.0 82 6.4 ■ [ 24.6 Il 10 5.0 91 5, p. 29.2 Il Comparative example]
4th 6.0 94 5.5 26.3 Il 96 5.3 20.6 It 95 19.8 93 13.4

As Table II shows, with an addition of benzoyl peroxide of less than 0.5 °, the impact strength of the hate obtained is hardly higher. As the amount of benzoyl peroxide increases, the elastomers are effectively crosslinked and the compositions obtained have improved impact resistance. This is due to the fact that, as a result of the formation of a crosslinked structure, the elastomers have a greater absorption capacity for impact energy, with

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the distribution of the graft polymer in the PVC is uniform. However, the amount of added Benzoylperoxyds 5 $ ^a or more, the "glass transition temperature" of the elastomer is extremely

high, the stability of the latex is adversely affected and the particle size of the elastomer ¹ becomes uneven. For this reason, the use of benzoyl peroxide in quantities of 5 ° or more is undesirable.

Examples 11-33

Crosslinked elastomers were prepared using, as indicated in Table III, the nature and amounts of the elastomers forming monomers and the organic peroxides used for crosslinking were varied. In the presence of 35 parts each of the elastomers was mixed with monomers 45.5 parts of styrene and 19.5 parts of acrylonitrile polymerized to give a graft polymer. The impact resistance values that of 15 parts of each obtained in the above manner Graft polymer and 85 parts PVC composite Dimensions are given in Table III. As comparative examples are the values for elastomers made with polyfunctional vinyl monomers are crosslinked, given in Table III.

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Table III-2

at
game Elasto - ,,, BA EHA Monomers for the elastomers ■ 20th 30 15 By-
oxide lot
By- Source
everlasting
index Blow
strength
(kg-cm /
cm) 19th ^mer MA EA PA 85 OA DA OMA DMA LMA HiA AN MAA AA St VCl DOPO 1.5 9.2 18.4 20th E-10 90 DTBPO 1.8: 13.6 23.4 21 E-11 80 10 30 10 BPO 3.0 5.7 22.8 O
O 22nd E-12 85 40 It H 5.1 " 21.3 «Ο
e » 23 E-13 50 30th Il 3.2 6.7 25.6 - * 24 Hisp 1 * f C.XJ 60 Il 1.5 10.6 23.2 25th S-15 BPB 2.0 9.2 19.2 26th E-16 30 30 55 : TBPA 4.0 8.4 18.6 E-17

I'orts. overleaf ■ " * &

Jatelle III-3

Bei- elasto- monomers for the elastomers per- amount .Quel- Sohlag-

game mer · _IiiÄ EA PA BA EHA OA DA OMA DIiA IMA MRiA AN MAA St ¥ 01 AA ^{oxyd Ρβ; ι>} Γ limgs-strength

index (kg-cm / ₉ cm)

«Ο« η co cn

27 E-18 70 65 80 20th 20th 30 ' 15th - 10 TBPO 3.5 5.4 17.2 28 E-I9 70 50 BPO 1.5 10.3 19.4 29 E-20 20th 20th 2.0 6.8 21.3 30th E-21 30th ti 1.8 9.2 20.6 31 E-22 100 dd ti 9.4 26.2 32 S-23 It 2.0 9.6 15.9 33 E-24. 100 11th 1.5 8.8 16.4

Ports, overleaf

Table II1-4

At- elasto- monomers for the elastomers per- amount source- impact-

spiel mer ivIA EA PA BA EHA OA DA OMA DMA LMA MMA AIT MAA AA St VCl ^ox ^ ^{ä Pero} ~ lungsfestigkeit

xyd index (, kg-cm / _o

Ver '. "..."

same- . .

Tseispßl

5 cf-1 ⁺⁵ 90 10 - - 13.2 10.8

0098 δ M. cf-2 ⁺⁶ 30th 85 10 15th H , 2 11th , 3 3 5/1 7 ' It cf-3 ⁺⁷ 50 16 , 0 10 , 4 8th "1 cf-4 ⁺⁸ 90 10 17th , 2 9 , 7

+ 5t cross-linked elastomer, which with is mixed polymerized ..

! ethylene glycol dimethaorylate '

+6: Cross-linked elastomer that is copolymerized with 1.8 fo divinyrbenzene »

+ 7t cross- linked elastomer that is _{copolymerized with 1 r} 7 $ ethylene glycol dixx kyimethaerylate »

+8: Cross-linked elastomer that copolymerizes with $ 1.5 bivinyrbenzene is.

12Ai Methyl aorylate EAi Ethyl aorylate PAf ii-propyacrylair BAi n-butyl acrylate EHAi 2-ethylhexyl acrylate OAi ootylaorylate DAi Deoxyacrylate QMAi Octyl methacrylate DMAi Decyl methaorylate LMAt Lauryl methacrylate MMAi Methyl methacrylate AHi ■; ■ Acrylonitrile AAi Acrylic acid MAAi:, '■; Methacrylic acid Stt ' Styrene vrnt Yinylchloria EPO Lauroyl peroxide 'BPÖi Benzoyl peroxide OPO Octaixoyl peroxide OHPOi Cyolohexanone Peroxide DOPOf DiQumylperoxy DTBPOt di-t-butyl peroxide BPBf Btttyl perbenzoate TBPAi t-butyl peracetate TBPOf t-butyl perootoate

As Table III shows, the use of an organic acetomtrsn crosslinked with an organic compound leads to excellent impact strength, whereas the use of a pale iron which is partially crosslinked by xytolrfcional monomers is leads to a Maaee whose sole

'QFHQiNAL

strength is hardly improved.

Examples 34-37

PVG (Geon IQ3-EP) and a graft polymer made by polymerizing 40 parts of styrene with 20 parts of acrylonitrile in Presence of 40 parts of caustic elastomer (E-6) after ^ Example 15 was obtained were mixed together, the mixing ratios of the "two constituents were varied" The mechanical properties of the mass obtained are given in Table IV.

Comparative Examples 10 to 13 show the properties of compositions which contain varying proportions of PVG and another graft polymer. In terms of its monomer composition, this graft polymer is identical to the crosslinked elastomer specified above and is not used (gel content 0 ^ ₁ practically the same part size as the crosslinked elastomer).

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Table I?

■ ^^^ properties Impact. Tensile strength PVC / graft ^. ·
polymer X _n ^ χ it uigJseiT
(kg-cm / cm ^) KeI υ η · ■
(kg / cm ^ ■ Comparative example
9 100/0 5.3 590 Example 34 90/10 18.6 480 Comparative example
10 10.2 420 Example 35 80/20 27.6 402 Comparative example Il 12.3 ^! 354 Example 36 70/30 34.2 360 Comparative example
12th H 11.8 270 Example 37 50/50 20.7 300 Comparative example
13th Il 9.2 240 y

Color IV shows that the composition, which contains PVC and a graft polymer, which was obtained using a non-crosslinked elastomer, has poorer physical properties, much if the mixing proportions of the two components are varied. On the other hand, it has been found that the composition according to the invention has particularly excellent physical properties, -if the graft polymer content is 10 to 30 $> ,

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Examples 38-49-

The impact strength values of compositions were determined which contain 80 parts of PVC and 20 parts of a gfcotifpolymeren obtained by polymerizing 65 parts of various monomers, as shown in Table Y , in the presence of 35 parts of crosslinked elastomers according to Examples 11 to 33 from Table V (In the table, 'X -D 3 \ -methylstyrene').

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Table T

pei
le .-, -; , 7 Pfro. α -
■ 0l.7K.er
'■■ τ.
ί " ^r erv / en-
..I · _; .. ,, 0- Grafted llonomers st MiA 20th ■ flf-MSt MAA AA ¥ 01 MA - 40 SA Blow
firm
speed
(kg-cm / _p
cm) Γ ^Γ * i
L. _ 70 10 22.6 i, Γ
j
-3 "2-5 10 90 20th 19.6 .. t
f
■ -> -. * C-4 B-6 80 30th 21.3 40 G-5 B-7 30th 40 30th 18.2 41 G-6 E-1.2 60 30th IO 20.4 ! 42 G-T E-13 40 40 30th 20th 23.2 43 G-8 1-6 60 10 27.4 G-9 E-15 60 28.6 Φ5 G-IO E-21 70 35 O 10 2Ό, 7th G-11 B-22 65 20th 31.2 * 7. G-12 E-3 40 40 24.1 Φ6 G-13 E-25 70 23.2 49

00983S / 1773

Example 50-53

60 parts of vinyl chloride were in a pressure vessel using potassium persulfate as an initiator in the presence of 4-0 parts of a crosslinked elastomer (in the form of a latex) which contained 85 parts of n-butyl acrylate and 15 parts of methyl methacrylate and which had a gel content of 945 ^ and one Had a swelling index of 6.7, polymerized. " The graft polymer formed was mixed in varying proportions with PVC (Geon I03-EP). The mechanical properties of the masses obtained in this way are given in Table VI. As comparative examples, the physical properties of compositions are given which contain PVC and varying proportions of a graft polymer by polymerizing 60 parts of vinyl chloride in the same manner as above in the presence of 40 parts of an elastomer (gel content 0%) with the same monomer composition as above but was obtained without crosslinking.

9835/1773

Part VI

Example no,

Content of graft polymer in the

Dimensions

Impact tensile strength Rockwell strength hardness (kg-cm / "(kg / _p (R) cnr) cm *)

Comparison "example

H o

Example 50 5 Comparative Example

15 «

Example 51 '10 Comparative Example

16 «

Example 52 15 Comparative Example

17 "

Example 53 20

Comparison "example - 18

5.3 7.4

6.5 17.3

9.4 20.8

10.6 22.6

13.2

590 116 533 110 510 108 492 106 436 101 418 "■ 98 375 93 386 94

314

86

As Table VI shows, the compositions according to the invention a high impact resistance and an excellent tensile strength as well as an excellent Rockwell hardness (R) in comparison with compounds that require the use of an uncrosslinked elastomer obtained graft polymer contain "

00983S / 1773

Examples 54-57

The physical properties of compositions containing different proportions of the graft polymer according to Example 2 and chlorinated PVC with a chlorine content of 65 ° (obtained by chlorinating PVC * Geon 103-EP) are given in Table'VII °

Table VII '

Example no,

Chlorinated graft poly- blow-heat PVC ($) mer W strength molded

(kg-cm / cm *) temperature (C)

Example 54 50 50 20.6 91.3 Example 55 70 30th 30.6 94.8 Example 56 80 20th 26.3 98.2 Example 57 90 10 17.6 101 Comparison
example 19 100 0 4.3 105

Table VII shows that even when using chlorinated PVG instead of PVC, a composition having excellent impact resistance can be obtained. On the other hand, she hates a graft polymer produced using uncrosslinked elastomer has low impact strength.

009035/1773

Examples 58-59

There were 'masses with PYC and with dem.naöh Example 2 used graft polymer (SI) or the graft polymer used according to Example 47 (G -. 1t) tested for impact strength after they were exposed to an "accelerated weather test. The' accelerated weathering test was measured using a ■ Weathemmeter type WE-2 (manufactured by Toyo Rika ^ Kogyo goc, Ltd. ") is performed" the results are given in Table VIII. Moreover, a preferred V _e rgleichsbeispiele the experimental results with a mass indicated, the PVC and a Contains graft polymer obtained in practically the same manner as (Gr-1) except that the elastomer was an uncrosslinked acrylate elastomer having the same monomer composition as the elastomer of (GI) (refer to Example 20). Furthermore, as a comparative example, a composition was used which contained PVG and a graft copolymer obtained in practically the same manner as in (GI), except that polybutadiene was used as the elastomer (comparative example 21).

009835/1773

Table VIII

example No. 21 Graft PVO /
polymer graft polymer Impact resistance according to be
accelerated ventilation
(ksD-cm / cm ² ) after
lOOStd » after
200h after
. 300h 80/20 0 +9 24.2 21.3 18.5 example 58 G-1 1 Il 27.6 ■ 26.4 22.3 19.7 example 59 G-11 Il 31.2 7.6 5.4 4.1 Comparison
example 20 cf-5 Il 10.2 20.0 15.6 8.3 Il cf-6 34.6

+ 9i impact resistance before accelerated ventilation

(Each example of Table VIII contains 1 part of dibutyltin maleate as a stabilizer per 100 parts of resin ingot Sample cf-6 contains an additional 1.5 parts of 2,6-di-t-butyl-4 ~ methylphenol, 'on 100 parts resin composition.)

As Table VIII shows, the impact resistance decreases that obtained using a polybutadiene elastomer Mass rapidly with increasing exposure time, whereas the impact resistance of the masses according to the invention can be seen clearly Decreased more slowly, which attf an excellent weathering ■ indicates persistence. ,

- Patent claims 0 09835/1773

Claims (1)

1. Polyvinyl chloride resin composition, ge ken η ζ ei ahnet durchi (A) 5 to 50 parts by weight of a resin (I) having the following composition tongue (A) 15 "to 60 parts by weight of a crosslinked elastomer (E), which was obtained in the following manner λ A solution of 0.7 "to 3 parts by weight of an organic peroxide with a decomposition temperature of more than 55 ⁰ C is in 100 parts by weight of bdtr na in at least one monomer of alkyl acrylates with Cj -O ^ Q-alkyl groups or a monomer mixture 60 parts by weight or more of at least one of these alkyl acrylates and 40 parts by weight or less of at least one monomer from the group acrylonitrile »acrylic acid, methacrylic acid, styrene, Al3ry! Methacrylate with Cj-C-jq-alkyl groups -and vinyl chloride, -below the decomposition" temperature of the organic ieroxyds polymerized in an aqueous Iiöeung, which a WasserlÖsliQhßn Eadikal- 'pol ^ triaattons ^ Initlatft ^^ eö φΜ iaiaa «stsne 70 # of the aenomers polymerized wÄi? tiin, Kforaaf the area Lattx outer Silhrenober- "*; - JaailJ dfr 2 # reetzung0tÄm |> eratur dee öjcgäniiichen will, and., - ".. ' (b) 40 "to 85 parts by weight of a polymer (P) that contains was obtained in the following way: At least one monomer from the group consisting of styrene, methyl or methacrylate and vinyl chloride KSSa is a monomer mixture from 60 parts by weight or more of at least one monomer selected from the aforementioned monomers and 40 parts by weight or less of at least one monomer. from the group of acrylonitrile, o ( -Me thy! styrene, methacryl acid, acrylic acid and alkyl acrylates with Cj-O-jq-alkyl groups are polymerized and (B) 50 "to 95 parts by weight of a resin (II) selected from the group or (c) a polyvinyl chloride resin 3EEÖL a mixed polymer resin 70 weight or more vinyl chloride and 30 weight steep or less of at least one monomer from the group vinyl bromide, vinyl menene chloride, vinyl acetate, Acrylic acid, methacrylic acid, alkyl acrylates with Ö <jH3.jq-alkyl groups, Alkyl methacrylates with G ^ -G ^ Q-alkyl groups ) and ÄthylenJ SSfi or Cd) resins obtained by chlorinating the resins (c) became· ' 2. ^ arzstoff according to claim 1, characterized g e k e η η ζ e i c h η The resin (I) was obtained by mixing 15 to 60 parts by weight of crosslinked elastomer (E) with 4-0 to 85 parts by weight of polymer (P). > 003835/1773 3 «resin composition nacli claim 1, characterized ke e g η η ζ η et verifiable that the resin (.1) by. Polymerization of 40 to 85 parts by weight of the monomer forming the polymer (P) ″ in the presence of 15 Ms of 60 parts by weight of crosslinked elastomer (E) was obtained. 4. Resin composition according to claim 3 »characterized g e.kenn, characterized in that the crosslinked elastomer (E) leaves at least 50? * Of an insoluble fraction when it was immersed in methyl ethyl ketone ^{at 3O 0 G for 48 hours.} 5. Resin composition according to claim 3, characterized ge k e η η ζ e i c h η e t, that the monomer which forms the crosslinked elastomer (E), 80 to 90 parts by weight of n-butyl acrylate and 10 to 20 Is composed of parts by weight of methyl methacrylate and that the monomer constituting the polymer (P) is vinyl chloride. 6 ", resin composition according to claim 1, characterized in that g e k en η, That the resin (I) was obtained in the following manner: Part of the monomer constituting the polymer (P) is in the presence of 15 to 60 parts by weight of the crosslinked elastomer (E) polymerized, whereupon the polymer formed is mixed with a separately prepared polymer so that the total amount of Polymer component (P) 4O to 85 parts by weight. 009835/1773 7. Resin composition according to claim 1, characterized in that the: Monomers that form the crosslinked elastomer (E), either at least one monomer from the group xethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, or a Monomer mixture of 60 parts by weight or more at least one of these alkyl acrylates and 40 parts by weight or less represents at least one monomer from the group consisting of methyl methacrylate, methacrylic acid, acrylonitrile and styrene, - "Λ ο Resin mass according to claim 7, characterized in that that the monomer that forms the crosslinked elastomer (E) from up to 90 parts by weight of n-butyl acrylate and 10 to 20 parts by weight of methyl methacrylate is composed, and that the monomer, • that the polymer (P) forms, from 0-100 parts by weight of methyl methacrylate, 0-40 parts by weight of acrylonitrile and 0 to Parts by weight styrene is composed (where the total amount of polymer (P) is 100 parts by weight). 9. A method for producing the resin composition according to claim .7, characterized in that the crosslinked ■ Elastomer (E) is made using benzoyl peroxide as the organic peroxide. 10. A method for producing the resin composition according to claim 7, characterized in that the crosslinked Elastomer (E) using at least one organic . Peroxides from the group lauroyl peroxide, octanoyl peroxide, 009835/1773 Cyclokexanoiiperoxide, p-chlorobenzoyl peroxide, dieumyl peroxide, di-t-butyl peroxide, butyl perTDenzoät, t-butylperaoetat and 1; -butylperoetoai will be produced" 009835/1773