DD143081A1 - METHOD FOR PRODUCING VINYL MIXING POLYMERS - Google Patents

Abstract

Process for the preparation of grafted Bsw, Copfropfpolymerprodukten by (co) polymerization of n-butyl and / or Äthyihexylacrylsäureester, optionally in admixture with others Vinylic monomers, such as vinyl chloride, vinyl acetate, vinyl isobutyl ether, Aorylic acid, - other (meth) acrylates, vinylidene chloride and the like, in the presence of powdery PVC substrates or aqueous PVC dispersions, under conditions of sorption polymerization, by adding such a monomer mass to the polymer substrate and the (co) grafting either at a pressure corresponding to one Monomarpartialdruck below the respective monomer saturation vapor pressure or at normal pressure under reflux conditions and, optionally with the addition of the consumed Moncmenuengen, to a polyaurylate bulk wax (a / ao) (ra polymerized Acrylic mass, mo - submitted PVC wet) from 0.05 to 2,

Description

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Title of the invention

Process for the preparation of vinyl copolymers

Field of use; the ^ indf g

The invention relates to a process for the preparation of vinylimine polyureas based on the polymerization of aorylates in the presence of polyvinyl chloride (PVG) and their preferred use as a PVC modifier »

Characteristic dea? known technical solutions

It is known, by polymerization of acrylic acid (AS), methacrylic acid (MAS) and / or various' (meth) acrylic acid esters on prepared PVC Sübstraten produce graft copolymers which have a number of improved properties over PYC in terms of transparency, impact resistance, weather resistance, Oberflächachenbeschaffenheifc etc (SPRAO and M. SAIITAPPA, J. Polym. Su. A, 16 (1968), 95).

Babei are both methods of radiation-initiated grafting of AS (Pr. 2311792), butadiene-methyl methacrylate (MMA) - or butadiene-AS mixtures (Fr. 1309809, DE_0S 1520456, 2606190) and alkoylacrylates and methacrylates in the vapor phase, as well as methods and technologies using radical-forming initiators. In the latter case, in addition to the pure alkyl acrylates (DB-OS 1694409), alkyl methacrylates (DI-OS 1801830, 1804049, 2014392, 2206179, GB 1099430) or multifunctional acrylate monomers, such as 1,3-butylene diacrylate (GB 1121997, GB 1295320), also Meth-ZAorylate / Gomonomer Misohungen used, acrylic monomers preferably mixed with styrene (GB 1304517)? • Acrylonitrile (R, M. BAUER and MS GUIUiOB ₅ Amer, Chesu Soc, Polym Chem Dion »Meeting * Los Angeles 1974, Polym, Preprints I _- I (1974), 1 397), butadiene (can 653574, GB 1039764, ref. 1351387), VC (US 3290265) or styxol / butadiene blends (US 3240843).

Furthermore, bees are in the grafting of ethylenically unsaturated monomers and particularly 1.3 ~ euf dry powdered PVC in the gas phase, d _s h "at a Monoaierpartialdsuok below the corresponding

Saturation vapor pressure ", acrylic monomers such as and acrylonitrile, can be grafted with a high grafting rate. (3Ξ-03 2056372) The PVC Speaialpolymere or corresponding molding materials obtained in this way have only a small improvement in important mechanical parameters on.

The disadvantage of the (meth) acrylate / PVC graft polymer products prepared by the known processes (Gemisoh eus the graft copolymer, PVC and homo-poly (meth) acrylate) is their limited application and processing ability »The naoh the different graft polymerization Although, largely using different Cosonomerer, obtained products generally have a number of improved mechanical and / or optical characteristics, but meet in terms of their overall appearance only a limited field of application for PVC molding compounds.

Other measures, such as the use of special multi-functional acrylic monomers - possibly in the form of different Oomonomermisohungen (GB 1121997, 1295320) - for the production of intimate graft copolymers, are expensive and also do not lead to optimal product properties.

Object of the invention

Bas object of the invention is to modify PVC by means of low Aoryiatantsile while lowering the technological effort with respect to improved mechanical, thermal and optical Mgensohaffcen.

Explanation of the essence of the invention - The technical task

The invention has for its object to develop a process for the preparation of vinyl copolymers by polymerization of acrylate monomers in the presence of PVC substrates and known radical-forming initiators in the temperature range between 30 and 100 ⁰ C under conditions of Sorptionspolymerisation.

Features of the invention

The object is achieved in accordance with the invention by introducing PVC, which is presented as a dry powder or as an aqueous dispersion containing conventional suspension and / or emulsion stabilizers, a composition of n-butyl and / or ethylhexyl acrylate, if appropriate with the addition of another ethylenically unsaturated compound Vinyl co-monomers, it is added that the (co) grafting in the sorbed monomer / polymer phase either at a pressure corresponding to a Monomerpartialdruck (p) below the respective monomer saturation vapor pressure (Ps) or - preferably in the polymerization in aqueous dispersion - at atmospheric pressure under Bückflußbedingungen takes place and, optionally with the addition of the consumed Monomemengen, up to a polyacrylate mass increase (MZ) in the limits between 0.01 and 2 is performed.

Preferably, the grafting of η-butyl or Äthylhexylscrylat alone; but for the purpose of special modifications, "such, B, increasing the adhesion when using the modifier tea PVC as Beschichiiungsmaterial u _e s' _s are Vinylcoraonoinere, vorsugs ^ else

 5

Acrylic acid (AS), methacrylic acid (MAS), the methyl or ethyl esters of both acids, and glycol mono-aoaurylate (GMA) or vinyl esters, in particular vinyl acetate (VAc), vinyl ethers, in particular vinyl isobutyl ether (VIBA '), vinyl or vinylidene halides, in particular vinylohioride (VC) and vinylidene chloride (VDC), and the like., up to a maximum of 50% _t based in an amount on the Gesamtmonomermasse used.

The resulting graft and Copfropfpolymerprodukte _f depending on the value for MZ, the ratio between grafted polyacrylic compound (m-mc) and submitted PVC substrate fair (mo), either directly or ηεο'η mixing with further. PVC - generally to a polyacrylate content between 0.5 and 10% by mass according to their intended Anwendungs- purpose - processed, are characterized in comparison to standard PVG especially by a higher flowability, transparency, surface texture (gloss) and z. T. improved impact resistance and thermal stability.

Application i

In a tempered Eeaktionsgefäß provided with a Eührvorrichtung and reflux condenser 100 parts by mass (MT) of a Sussex¬ sions PVC having a K value of Pikentscher of 60 and a plasticizer consumption of 25 mass% DOP (PVC-S 60) in an aqueous Ό, 08 Mass-JS-igen Methylhyd.roxyäthylo © lluloselösung (S 60 / S) submitted.

Ban & ch becomes the oxygen-flushed reactor 0.2 M diisopropylperoxidioarbonet (BIPP) and 15 MT η-. Butyl acrylate (BA) added and to a temperature of 60 ⁰ C ervjärrat and 2 h under Hückfluß (under Kormsldruok in the open system) polymerized.

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Bas from the suspension separated, washed and dried Graftpolymerprodultt with a MZ of 0.1 has a melt index i of 4.6 g / 10 min * (according to TGL 20968) and a thermal stability (TS) according to oven test (TGL 28475) of 35 min , Of the total of 5% by weight of polybutyl acrylate (PBA) mixed with PVC-S 60 graft polymer product, the impact strength (KSBF according to TGL 14068) determined:

KSBF 0 ⁰ C _e . 9.6 kJ / m ² KSBF 20 ⁰ O .. 23.0 kJ / m ²

Bas grafted polymer product is also particularly suitable for improving the deep-drawing ability, transparency and surface gloss of PVC films.

1 mm press films prepared from PVC-S 60 containing 1% by weight of PBA have a light transmission (D) of 84 % (based on absorbance measurements, at a wavelength of 589 nm) _β

In addition, the total of 1% by weight of PBA-containing PVC-S 60-NoHormallmasse increased impact strength (ESBF at 20 ⁰ C = 5 kJ / m ² ).

Other graft polymer products are obtained by varying the feedstock (PVC substrate, monomers (s), initiator type and concentration) and the polymerization conditions, the temperature (T) ₅ Brück (polymer; ion under reflux, d, h _s at atmospheric pressure in open system, or above the 'normal pressure imtsr conditions, p / Ps <1)

In addition to the discontinuous driving regimes (generally up to values of MZ ~ 0.1 "to 0.15), (co) grafting can also be carried out, under continuous monomer feed, generally for MZ> 0.2, where the p / Fs Ratio is kept substantially constant over the polymerization space.

The following graft substrates have been used:

PVG-S 60 as a dry powder with an average particle size of 110 / .m (S 60), as a suspension with an average solids content of 32% by mass and 0.08% by mass of methylhydrogen oxycellulose (S .60 / B) ;

- PYO-S 69 (S 63, S 68 / S);

- An emulsion of a PYO with a K value of Fikentscher of 62 and a solids content of 32 pigs (S 62 / B).

As initiators have been used:

Biisopropyl peroxydicarbonate (DIPP),

2,2 ^f -Azobis (isobutyronitrile) (AIBN),

Biauroyl peroxide (DLPO),

tertiary Amyiperneodecanoate (APD),

Copfropfmonomere for BA and Äthyl.hexylaorylat (AHA) are ± n a mass between ca, 10 and 40 % ^ related to the Gessmtinonomerenmesse used? Aorylsäijsre (AS)

Methyl diethacrylate (MiA)

Vinyl chloride (YG)

Vinyl isobutyl ether (YIBA)

Crlykolmonoaorylate (GääA)

Vinyl acetate "(VAc)

"The graft and Copfropfpolymerprodukte listed in '; Tab. I, the graft monomers used at different Polymerisetionsbedingungen (pressure normal pressure (N.) or overpressure according to the specified p / Psj'Tj initiator type and concentration in MT / 100 MT PVC substrate j Specification of the monomer mass ratio when using a comonomer) either by discontinuous (MZ ^ = 0.15) or semi-continuous polymerization (MZ> 0.15) have been produced j document with the specified properties for the corresponding PVC Pormmassen (if no particular data - blended to a total of 3 % by mass of poly (ylatoate) / i ", TS and ESBF, to 1% by weight polyacrylate / determination of D) ranges and effectiveness of possible PYC modification.

Table I

No, Polymeris. Conditions T Pressure Initiator ( ⁰ C) (p / Ps) (% by mass) N. O 2 DIP? PVC S exercises. 60 / S Moncmeres (Massesa-vero) MZ is (S / 10 min) TS (mia) B (J) KSBF 0 ⁰ G _o (kl / nT) 20 ⁰ C ! 1 60 N. 0.5 APB S / 60/8 62 / E BA 0.10 4.6 35 84 9.6 23.0 O CVI 70 N, 1.0 AIBN S 60 / S BA 0.28 38 10.2 22.8 ί 3 50 N. 0.3 DIPP S 62 / S BA 0.25 3.2 78 m 4 65 N ₀ 1.0 AIBN S 60 AEEA 0.18 32 10.5 24.5 5 55 0.80 0.4 APD e 60 / S AEHA 0.22 5.8 75 6 60 0.75. 0.2 DIPP S 68 BA 0.09 3.2 82 7 55 0.82 0.5 DLPO S 68 / S BA 0.12 3.6 38 8th 65 0.76 1.0 AIBN S 68 / S BA 0.18 73 8.8 1S _S 5 9 70 O ₉ 85 0.3 DIPP S 68 / S BA 0.10 2.8 86 10 55 N. 0.1 DIPP S 60 / S BA 0.25 4.8 10.2 25.5 11 70 N. 0.2 DlPP S 62 / S BA 0.06 3.8 32 82 9.8 26.2 12 60 N. 0.6 AIBN S 68 BA 0.12 30 9.2 23.6 13 60 N ₀ 0.5 APD e 60 BA 0.10 2.8 80 14 65 N. 0.5 DLPO S 60 / S AEHA 0.18 3.8 78 9 * 5 23.7 15 60 N. 0 * 2 DIPP S AEHA 0.20 82 8.7 20.5 16 55 S 3 BA / AS 0.18 4.2 72 8.2 20.5

No · Polymer is · condition not determined T Druok initiator ( ⁰ G) (p / P3) (mass ~%)

FVO Sübst,

Monomerθs

(Msssen ~

ver ·) MZ is TS D (S / (min) (*) min)

IISB?

17 60 N. 0.5 BLPO S 60 4 BA / 1 MMA 0.20 3.2

18 65 N. 0.7 AIBN B 62 / B 3 BA / 1 VC 0.12 3.0

19 70 0.80 0.5 APD S 60 / S 4 BA / 1 VIBA 0.12 3.2

20 60 0.75 0.3 DIP S 63 / S 3 BA / 1 QAA 0.24

21 65 N. 0.2 DIP S 68 3 ÄHA / 1 VO 0.12 4.2

22 60 N. 0.5 APD S 68 / S 4 EHA / 1VAc 0.14 4.5

23 70 N. 0.5 DLPO S 60 3 ÄHA / 1 (MA 0.18

24 70 0.82 1.0 AIBN S 60 / S 4 ÄHA / 1 AS 0.24 3.2

48

48

72

75 82

80 85

(Kl / af)

O ₀

8,7 8 _B 6

7,

19.8 20 ₉ 5

17.8

Claims (2)

Inventions 1. A process for the preparation of Vinylmisohpolymerö duroh polymerization of Aorylatmonomeren in the presence of PVC-8ubstraten and known radical-forming initiators in the temperature range between 30 and 100 ⁰ C in conditions of Sorptionspolymerisation, characterized in that PVC, which as a dry powder or as aqueous, conventional suspensions If such a mass of η-butyl and / or Äthylhexylacrylat _{f is} optionally added with the addition of a further ethylenically unsaturated vinyl comonomer, that the (co) grafting in the sorted monomer / polymer phase either at a pressure corresponding to a Monomerpartieläruck below the respective Monomatenättigungsdampfdruckes or - preferably in the polymerization in aqueous dispersion ~ at atmospheric pressure under reflux and, optionally with the addition of the spent Monoraermengen until led to a Polyaorylat-Massenenzuwacha in the boundaries between 0.01 and 2 2. The method according to item 1, characterized in that the graft monomers η-butyl and Äthylhexylacrylat in admixture with at least one other VinylcoiGcnomeren, preferably acrylic acid, methacrylic acid, the methyl and ethyl esters of both acids and glycol monoacrylate or vinyl esters, in particular vinyl acetate, vinyl ethers, in particular Viaylinobutyläther, vinyl or vinylidene halides. in particular Vinyl chloride and vinylidene chloride, in an amount up to a maximum of 50%, based on the total monomer mass, are used Process according to points 1 and 2, characterized in that the graft and Copfropfpolymerprodukte either directly or after Abxaischung with other PVC - in general to a polyacrylate portion 0.5% and 10% by weight according to their predetermined AnwendungszYjeckes - are processed *