DE2064297A1 - Process for the production of vinyl chloride resin mixtures - Google Patents

Description

P ΛΤΕ. ΝΤΛNWA.LT

DR. HANS ULRICH MAY

D 8 MÖNCHEN 2, OTTOSTRASSEIa O Π C / 9 Q

TELEGRAMS: MAYPATENT MUNICH ZUDhZ3 /

TELEPHONE CO81O OSSO82

GpA 111 / e Munich, December 29, 1970

Dr M /

S-19-P-17/920

Shinetsu Chemical Company in Tokyo / Japan Process for the production of vinyl chloride resin mixtures Course summary (abstract) of the invention

According to the invention, a vinyl chloride resin mixture is produced, by 1) in a two-line polymerization vessel, which is a previously prepared aqueous emulsion contains, continuously through one of the feed lines 10 to 90 parts by weight of diene rubber polymer and through the other feed line initially 10 to 80 percent by weight of a total amount of 90 to 10 parts by weight of methyl methacrylate and then a Ge » Mixing the remaining methyl methacrylate and 180 to 5 parts by weight of styrene are added and polymerized, 2) the graft polymer prepared in this way is obtained from the aqueous emulsion and 3) then 30 to 1 part by weight of the graft polymer are added with stirring, below 70 to 99 parts by weight of vinyl chloride resin. The hars mixture obtained supplies

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processing a stiff product of better transparency and impact strength, which is home wrinkles KAVM any white Knicfciinie "isplays"

Description of the invention

The invention relates to a method for the production of Vi ~ nylon resin «mixtures» which have better transparency and Impact resistance «own and foils provide that when folding hardly show any white kink line »

To improve the impact resistance of rigid or stiff products »» products made of vinyl chloride resin is already known, the vinyl halide har » to add suitable Harae * For example, so-called ABS Hara, which is made from butadiene, styrene and acrylonitrile or Acry! Ester is added to the vinyl chloride resin. »However, show those from such Vinyluhlorldharsmischungen with a content products manufactured on ABS-Harg have an unsatisfactory office leakage, and films made therefrom give white crease lines when folded, although the impact resistance is improved isο if on the other hand aie transparency and bad .Folded stapling of the products is improved, the Impact resistance, so that no products have been manufactured to date could be, which on the same side have a superior impact resistance, Have transparency and bending properties »

Biu'ch the invention, a method ssur manufacture will now be made of new Vinylohloridharamisctsungen which do not have AEIE usually observed mentioned disadvantages.

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have better transparency and impact resistance and provide films which hardly have white crease lines when folded demonstrate"

According to the invention, this object is achieved by a method for the production of Vinylchloridharemiechungen, which thereby is characterized as being one in a polymerization vessel contained, previously prepared aqueous emulsion Continuously, but separately 10 to 90 parts by weight of diene rubber polymer and initially 20 to 80 percent by weight of a total · » inetige from 90 to 10 parts by weight of methyl methacrylate and then a mixture of the rest of the methyl methacrylate and from 180 to 5 parts by weight of styrene are given, after the end of the polymerization, the graft polymer produced from the aqueous emulsion obtained and 30 to 1 part by weight of the same with stirring to 70 to 99 parts by weight of vinyl chloride « to be given resin "

The method of the present invention has been found in the following manner: Based on studies of mixtures of vinyl chloride resin and various graft polymers with diene rubber polymer as the main chain, it was concluded that in order to improve the impact resistance of the molded products made from the mixtures, the graft polymer must have rubber-like elasticity, and it has been found further, that if the graft polymer used was uniformly grafted and contained an equal amount of free polymer, that it was was compatible with vinyl boride resin, the mixture of vinyl

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chloride resins and such a graft polymer are not just one has excellent transparency, but also when splitting there are no white corner lines. Further investigations enabled the production of such graft polymers and the solution of the task at hand *

When performing the fittings according to the method, the graft polymer which is mixed with the vinyl chloride resin is produced from 10 to 90 parts by weight of diene rubber polymer, 90 to 10 parts by weight of diethyl methacrylate and 180 to 5 parts by weight of styrenes continuously, but separated by two different feed lines, into a polymerisation vessel eu of a previously prepared aqueous emulsion * to carry out the polymerisation.First, 20 to 80 percent by weight of the total amount of the methacrylate is added and, after the reaction is essentially over, the hurry is the Methylmethacj? ylats _f corresponding $ 0 to 20 Gev / ichtsprossent d @ r total amount "and the specified styrene au of the Fi'rüpfpalywer enthalteoäen Bsiillaictt Bugegebeae Bas eo produced 3? fropfpolyme2 · let Biem * lent evenly grafted" and la contain him a lot of free polymer is sufficiently "®Ò it HaB with VlqarlehXoridluuro sufficiently compatible lat · Me öriafle aafUr Sins vesmiitUeh the following

Ι «) Dienköutschtikpölymer t» a itettylnettoexylaiHMHiemer © iej *

An ionomer mixture of methyl methacrylate and styrene are continuously separated, however, from aqueous solutions

109827/178 4

added so that fresh Dleökautochttkpolymer and the monomers are always present in the Polyaerisationsraediura. stage of this polymerization process iat relatively slightly free polymer present, which avoids excessive build-up of the grafting reaction, while later The course of the polymerization shows the gradual reduction in the concentration of the smulsifier in the reaction liquid, see below leads to an extraordinarily large reduction in the occurrence of free polymer, which prevents the reduction in the grafting reaction and thus results in this process Graft polymer receives a uniform degree of grafting, 2) If, as mentioned above, some of the methyl methacrylate by itself and then the remainder of it is added together with styrene, the graft polymer produced is not excessively polar and is therefore, as desired, compatible with Vinyl chloride resin *

In the following, the method according to the invention is described with others Described details?

For the production of the graft polymer should be the one in the first Process stage, the amount of aqueous emulsion used is expedient References are chosen so that the graft polymer produced is present in the reactant liquid in a concentration of 40 to 50 percent by weight. To prepare such an aqueous emulsion, 0.1 to 10 parts by weight of an emulator is added to 100 parts by weight of water, followed by the above specified amounts of the constituents of the polymer are added to the mixture, Various types of known emulsifiers

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are usable. Of these, an emulsifier, as is known for diene polymers, such as disproportionated resin soap, tetrabydrozoietin soap, dextropimar soap or laury soap, is particularly advantageous, examples of the diene rubber polymer added to the aqueous Enmlsiöii are polybutadiene or made from at least 50 # butadiene and styrene. styrene copolymer _e the amounts of diene "above rubbery polymer and Methylmethaorylat or a mixture of methyl methacrylate and styrene have separated and kontlnuier" borrowed in the PolymerisationsgefäB be given. If the quantities are not within the specified ranges or if the two components are before the? Addition are mixed, the object of the invention is not achieved. As a result, when carrying out the process according to the invention, a polymerization vessel with at least two lines for one and the other of the two constituents must be used. The amount of styrene added in this polymerization is preferably 0.5 to 2 times the total amount Methacrylate used to carry out the process, the polymerization is carried out for 2 to 10 hours at 40 to 70 ⁰ O in the presence of known polymerization catalysts, preferably in the presence of the so-called redox catalyst, which is made from a peroxide such as cumene hydroperoxide or diisopopylbenzoyl peroxide, and a sisene salt like Blsen-XX-Sulphate *

In the second stage of the process, the graft polymer produced is obtained, filtered off and dried using the well-known method using alluvial ice.

109827M78 *

Then, in the third stage, the procedure becomes the free Polymer-containing graft polymer coated with Vieylchloridhars » The amount of the graft polymer in the mixture must not be too small, since aonet does not achieve the aim of the invention will, on the other hand, not be too great, since in the « In this case not only reduces the impact resistance of the product, but also the characteristic properties of vinyl chloride »are worsened. From 99 to 70 parts by weight of vinyl chloride are therefore added to 1 to 30 parts by weight of graft polymer. In this way, vinyl chloride resin mixtures are obtained, which are rigid products with high impact resistance (due to the rubber elasticity of the graft polymer) and Provide superior clarity and freedom from white creases when folded (due to the presence of the free polymer) "

The erfind nngsgetoäß su used vinyl chloride bar se are not only limited to vinyl chloride homopolymers "but KTTN * - nen aas the group of copolymers be chosen from at least 80 i> vinyl chloride and other copolymerizable vinyl monomer such as vinyl acetate, acrylonitrile, vinylidene chloride, vinyl ethers and" tr-olefin, manufactured bind,

When the degree of polymerization of the vinyl chloride hareee eu hooh It is difficult to make a rigid product from it without an additive are made by plasticizer (s) "If, however, the polyne" If the degree of risk bu is low, you will hardly get any product with high mechanical strength. Ss is therefore advised that

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—6 ** »

Select degree of polymerization in the range from 600 to 1300 see below * Dae evenly mixing the vinyl chloride and the graft polymer ISIBt easily using a for such purposes commonly used device, e »B <> of a Waleenaisohere or an Innenmiechers, perform.,

The following examples explain the invention o all therein indicated ropes and percentages refer to weight. To determine the iodine impact strength, test pieces such as is made as follows:

A mixture aua 100 parts of a VinylchloriäharBgemisches _β ■ * ■ 2 parts Dibutylelnnraaleat, 1 healing dibutyltin dilaurate! And 1J5 Hellen butyl stearate for 5 minutes kneaded at 160 ⁰ O to orphan "su a plate shaped and this for 10 minutes at 170 ⁰ C under a Brack of 200 kg / cm pressed * the thus prepared plate was subjected at 23 ⁰ C of the test according to ASTM-D-256 "whereby one would obtain the value of the Issod-SehlagBähigkeit the respective Vinylühloriöharamisohang

Example 1. Zn one equipped with a stirrer and two feed lines Polymerization vessels were 100! Parts of water and 0 * 5 parts of the «

proportioned hara soap given as an emulsifier and added to

₀ stirred 65 0 / rum to produce an aqueous emulsion. Then was through one of the leads uniformly over 5 hours, a mixture of (a) 80 parts of styrene-butadiene copolymer (? 23.5 and 76.5 &# styrene butadiene) having an average particle size of 08 0 _t | M "una a Peatstoffgehalt of 52 % and (b) 0.047 parts

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len ~ £ isen XI sulfate added, while sägegeben uniformly over 2 Standen a mixture of 17 parts Kethylmethacrylat and 0.17 hone cumene hydroperoxide through the other supply line "During the Zulaufe the two mixtures, the polymerization at 65 ⁰ O was carried tthrt . To the end of the polarization, a mixture of 17 parts of methyl methacrylate, 34 parts of styrene and 0.5 part of cumene hydroperoxide was added to the emulsion containing the polymer over the course of 3 hours and polymerized at the same temperature during this addition, which was terminated In this polymerization, 50 parts of a 0.5 percent strength aqueous calcium chloride solution were added to the emulsion containing the polymer in order to salt out the graft polymer, which was then filtered off, washed and dried. The yield of the product was 99.5 t,

10 parts of the graft polymer were mixed with 90 parts of polyvinyl chloride with a polymer degree of 800, and the physical properties of the product obtained were determined. The impact strength of the aemisohes was 22.5 ft * lb / in · Sample foils made from the solution wa « transparent and showed no white crease lines when splitting *

Example 2

In a polymerization vessel like that used in Example 1 an aqueous emulsion was added, which consisted of 100 parts of water and 0.2 parts of disproportionated Hareseife,

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.10-

and a mixture of (a) 43 fine polybutadiene with an average partial ohmic diameter of 0.25 μm and a synthetic material content of 58% and <b) 0.047% bis-X-sulfate, and the optionally a mixture of 17 parts and 0.17 parts Methylmetheorylat Diieopropylbeneolhydroperoxid by the other connection evenly over 2 STUN '', while dee Zulaufe the two mixtures, the polymerization was performed at 65 ⁰ O by "Anschliesaena, after the end of the polymerization, ₉ , a mixture of 17 parts of methyl methaorylate, 41 parts of styrene and 0.5 part of diisopropylbenosol hydroperoxide was introduced into the aqueous emulsion containing the polymer uniformly over the course of 3 hours and polymerized ^{at 65 0 O} 1 obtained, and it was a vinyl chloride-vinyl acetate copolymer with a Polym in various ratios erization degree of 800, aaa consisted of 5 # vinyl acetate and 95 ° h of vinyl chloride, given "The physical properties of the products thus obtained are given in Table 1"

Table 1

Ratio (parts)

Vinyl · - Pröpf « ohlorid- poly · »her» mer

Physical properties

ecbaften

Schlagaä- through- appearance authenticity of the pieces (ftolb / in) after folding

invention
invention
Invention 2-1
2-2
2-> 90
8tf
70 10
20th
30th 20, t
22.5
21.2 Well
Well
XUt unchanged
unchanged
unchanged comparison 2-4 50 50 7.0 advertised White

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Comparison 1 _Ö

In a polymerization vessel equipped with a stirrer, 80 parts of an otyrene-butadiene copolymer such as that used in Example 1, 0.5 part of disproportionated bar soap, 0.04 part of iron-XI substance and 100 parts of water were added at the same time ₍ and then A mixture of 34 parts of methyl methacrylate, 34 parts of styrene and 0.67 part of cumene hydroperoxide was added to ^{the mixture in the course of 5 levels and polymerized at 65 °} C. The graft polymer thus produced was obtained as in Example 1.

10 parts of the copolymer thus prepared became 90 parts Polyvinyl chloride mixed with a degree of polymerization of 600, and test pieces were produced from the mixture » These showed an impact strength of 10.1 ft.lb / in as well as a significantly poorer transparency and gave white knee lines when splitting »

Comparison 2 "

80 parts of styrene-butadiene copolymer such as the 0.3 part of disproportionated Hareseife used in Example 1, 0.047 part of iron II sulfate and 100 parts of barrels were added to a polymerization vessel equipped with a stirrer and mixed well optionally wherein the polymer containing a Bmolsion MIbοhang of 34 hone Methyloethacrylat, 34 parts of styrene and 0.67 parts CuBolhydroperoxid, and it was polymerized at 65 ⁰ C for 5 hours. The graft polymer obtained was obtained as in Example 1. 10 parts of it were

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with 90! bearings polyvinyl chloride with a degree of polymerisation of 800 mixed, and test stacks were made from the mixture ο These showed extremely poor transparency and white lines when folded. Their impact was 2.5 ftolb / in "

Comparison 3 _e

80 parts of a styrene-Butadiest "Gopolymers as that used in Example 1, O ₉ 3 parts of disproportionated resin soap _# 0.047 parts Eieen II Sutlfat and 100 parts of water were well mixed _{and the mixture was uniformly through one of the leads and continuously course of 5 hours in a vessel equipped with a stirrer Polymerisationagefäfi poured while equilateral continuously eugegeben by the other connection in the course of 3 hours, a mixture of 17 parts of styrene and O ₈ 17 parts of cumene hydroperoxide wast the polymerization was carried out in this way at 65 ⁰ C The graft polymer was then obtained from the reaction fluid as in Example 1 "10 parts of the graft polymer were" mixed with 90 parts of polyvinyl chloride with a degree of polymerization of 800 "and test pieces were produced from the mixture." These showed extremely poor transparency and gave when splitting white knee lines, thre beating shanks gkelt was 3.9

Example 3

80 parts of styrene-butadiene copolymer and methyl methaoryiat and

Styrene in the amounts given in Table 2 were as in

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.13-

Example 1 polymerized. 10 parts of the graft polymer produced were mixed with 90 parts of polyvinyl chloride with a degree of polymerisation of 800 Table 3 specified physical properties »

Table 2

I ₀ fabrics (Te ^ iIe) 2nd stage (Parts) 34.0 attempt
Kr, Methylmeth-
acrylate Styrene Methylmetal · »styrene
aorylate 34.0 Invent
tion 3-1 6.8 0 27.2 34.0 »3-2 27.2 0 6.8 0 «3-3 17 * 0 0 17.0 34.0 Ver
equal to 3-4 0 34.0 34, o 6.8 3 · 5 34.0 0 0 27.2 "3-6 6.6 27 ₉ 2 27.2 17.0 «3-7 27 _e 2 6.8 6.8 34.0 "3-8 0 17.0 34.0 » 3-9 4 _e 0 0 30.0

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Ver
search
Mr. Impact
ability
(ft.lb/in) -14- 2064297 3-1 17 ₈ 6 ! Table 3 3-2 17.6 Bwohslehtigkelt Appearance of the
Test piece
after folding Invent
manure 3-3 23 _$ O Well unchanged η 3-4 18.5 Well unchanged η 3-5 5.5 God ttttver & changed Ver
same 3-6 3.9 opaque considerable white W. 3-7 to, t sdemlloh opaque know something η 3-8 13.5 opaque considerably weld. W. 3-9 8 _P 7 eiemlloh opaque knows something N - 4th opaque ernebllch knows dd opaque something vei6 example

In an experiment similar to that described in Example 1 disproportionate Harelfe replaced by Laurylseifa and Styrene-butadiene copolymer »methyl ethyl aylate and styrene in the Polymerized amounts given in Table 4. 10 parts of the graft polymer obtained from the HeaktlonsflUesigkelt with 90 parts of polyvinyl chloride having a degree of polymerization from 800 mixedο The physical properties of the mixture are given in table 5 «

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▼ he
each
Mr. ₀ Tabel 4th 45.0
17.0
25.0
5.0 2nd stage 4-1
4-2
4-3
4-4 1.
free Fabrics
Ie) 47.5
2.5 StyrpiL 4-5
4-6 Styrene btt
tadien-öo-
polymer
(Peotatoff) 90.0
34.0
50.0
10.0 invention
N
H
M. 10.0
25.6
50 _f O
90.0 95.0
5.0 Ver
same 5.0
95.0 Methyl ethyl
aeth- aeth-
acrylate acrylate 45.0
17.0
25.0
5.0 47.5
2.5

Table 5 Suggested »» - Aaesehen -de «

also ability transparency PrQfstOoke Arο (ft.lb/in) after aging

Brfin
manure 4-1 1β, 5 God unchanged N 4-2 22.5 Well unchanged M. 4-3 25.3 Well unchanged m 4 ~ 4 20.0 sieotlioh
opaque know something

comparison

4-5 4-6

7.5

10.0

God opaque

unchanged considerably white

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Claims (1)

-te- 2 O 6 4 29 7 Pa te flt a de ρ T ₁₁₁₁ U ₁ G he Process e> «r production of vinylolilorid ^ Harsaisehungeifc, characterized by the fact that a Sfrapfpolymer is produced by continuously and simultaneously, ^ edooh separated into a stream produced aqueous seralsion ₉ other 10 to 90 parts of Bienkantechtikpolywejf and on the other hand a total amount of 20 to 80 weighted iron 90 to 10 parts by weight of methacrylate as well as snsohlielend @lne Mieobcog the remaining methyl methacrylate and 180 to 5 parts by weight of styrene are added and polymerized 50 to 1 parts by weight of the graft polymer zvL ? 0 to 99 parts by weight of vinyl chloride aar 2. ssh are given «. Method according to claim 1 «characterized in that as Oienic skin polymer a butadiene polymer from the Q-type Polybutadiene and by polymerizing at least §0 ^ Butadiene and styrene made butadiene-styrene copolymers is used" Method according to claim 1 or 2, characterized that the aqueous emulsion through the suspension of O ₉ I Me W '1 ■ How to share an Emmlgatore eu 100 manufactured 109827/1784 Process according to one of the claims 1 to 3, characterized in that the graft polymerization takes place for 2 to 8 hours at 40 to 70 ⁰ O in the presence of a redox catalysis. gates is carried out. Method according to one of Claims 1 to 4; characterized! that a vinyl chloride homopolymer or a vinyl chloride copolymer prepared by polymerizing at least 80% by weight of vinyl chloride and other copolymerizable vinyl monomer is used as the vinyl chloride resin « 6a Process according to one of Claims 1 to 5, characterized in that the vinyl chloride resins used have a degree of polymerization of 600 to 1300 ₃ 7 «Process according to one of Claims 1 to 6, characterized in that the amount of styrene used is 0 _P 5-bia 2 times the total amount of methyl ethyl aorylate, BATH ORIGINAL 109827/1714