CN101481487A - Spray drying polymer for PMMA plasticized sol with improved storage stability - Google Patents

Abstract

The invention relates to a copolymer of methyl methacrylate and butyl methacrylate as a plastisol in the automobile field and as a ground coating. The invention describes an approach to improve the stability of the plastisol by applying a small amount of crosslinking agents, which remains to attain the mechanical performance of the partially-crosslinked plastisol.

Description

Be used to have the spray-dired polymkeric substance of the PMMA plastisol of improved stability in storage

Technical field

The present invention relates to based on the plastisol of plastifying PMMA polymer composition by adding softening agent, described PMMA polymer composition also comprises the bridging property component in addition.

Background technology

Plastisol, the i.e. two-phase system of forming by plastic pellet or synthetic resins particle and the softening agent that is fit to or suitable plasticiser mixture, can prepare by various plastics in theory, yet industrial most important applications still is limited to a spot of polymeric system so far.The multipolymer that is formed by polyvinyl chloride and other ethylenically unsaturated monomers is known and is used widely.Disadvantageously their cl content, this chlorine may play erosion action under given conditions.Described plastisol is also known with title PVC-plastics, plastisol, organosol or plastogel.(also referring to Ullmann ' s Encyclopedia of IndustrialChemistry (Liv Ullmann technical chemistry complete works), the 5th edition, A 21Volume, the 734-737 page or leaf, VCH 1992; Becker-Braun, Kunststoff-Handbuch (plastics handbook), the 2nd edition, the 2/2nd volume, the 1077-1090 page or leaf, C.Hanser 1986; People such as H.F.Mark compile, Encyclopedia of Polymer Science ﹠amp; Engineering (polymer science and engineering complete works), the 2nd edition, augment volume, the 568-643 page or leaf, Wiley-Interscience 1989 and Saechtling, KunststoffTaschenbuch (plastics pocket book), Carl Hanser Verlag, M ü nchen, the 26th edition, (1995) the 406th pages and the last few pages).

Based on the multipolymer of methyl methacrylate and butyl methacrylate, so-called PAMA plastisol is used for the plastisol of automotive field very successfully.Described plastisol is as bonding plastisol, sealing agent, welding flux and chassis protection composition and floor covering.Yet also from just there being plastisol to use (referring to DE-PS 934 498, FR-A 2,291,248) for a period of time for practice based on acrylate.Last-mentioned prior art is based on the recognition: need between the two harmonious of glass transition temperature Tg, size of particles and the composition of polymer particle on the one hand and special on the other hand softening agent to be used to prepare industrial acceptable PAMA plastisol.

At this, the rule of making is, the glass transition temperature Tg of polymkeric substance is low more, and the average particulate size of polymkeric substance should be big more.The average particulate size of the polymkeric substance that uses must be between 0.1 μ m and 500 μ m according to FR-A, and should be preferably between 0.3 and 20 μ m.Proposition with suspension polymerization and acrylic polymers letex polymerization all as suitable primary particle.

It is the PAMA-plastisol that preferably has alkaline comonomer of 0.1 to 200 μ m that DE-A 25 43 542 has described particle size range equally, and described plastisol preferably obtains as emulsion polymer.Particularly preferably be 0.1 to 20 μ m, especially be the particle of 10 μ m to the maximum, however according to the disclosure document only to prepare by letex polymerization.The another kind of variant of PAMA plastisol has been proposed in DE-A 2,772 752 and 29 49 954.Be the core-shell polymer of the shell of consistency herein with the nuclear of plasticizer compatbility and relatively poor plasticity.At US-A 4,558, the plastisol based on the multipolymer that is made of methyl methacrylate and methylene-succinic acid or itaconic anhydride has been described in 084, verified its has good especially adhesivity on the pretreated metallic surface of electrophoresis.Floor covering based on the PAMA-plastisol has been proposed in the recent period, wherein application of pure polymethylmethacrylate (PMMA) is as body material, described polymethylmethacrylate part is with the emulsion polymer form, and part is used (DE-A 39 03 669) with the suspension polymer form.

As pointing out among the EP-A 477 708, can be by the pearl polymerization product of using spray-dired polymeric dispersions simultaneously and in suspension polymerization, obtaining, wherein at least a is methylmethacrylate copolymer, obtains to have the plastisol of improved product quality and big range of application.

Other work in PAMA-plastisol field are used to improve the especially adhesion strength on metal substrate, for example the polyamide resin (polyaminoamide) (referring to EP-A 533 026) by using 2.5-10 weight % simultaneously.The EP-A 121.759 same polyamide resins of recommending are as the protective colloid that is used to improve the plastisol storage stability.Other open source literatures are intended to improve adhesion property, for example (US-PS 5 by introducing in the PAMA-polymkeric substance especially (methyl) glycidyl acrylate, 120,795), or by introducing Propenoic acid, 2-methyl, isobutyl ester improve plasticizer compatbility as comonomer (EP-A 477 708; EP-A 539.031).DE-OS24.54.235 (Teroson GmbH) has described the uncrosslinked plastisol of being made by methyl methacrylate and butyl methacrylate and has protected thing as the chassis in the automobile making.DE-OS25.43.542 (R

GmbH) the uncrosslinked multipolymer of being made as adhesion promoter by methyl methacrylate and butyl methacrylate and vinyl imidazole has been described.Chalk as filler, is used for plastisol the coating of metal.DE-OS 28.12.016 (du Pont) has described the non-aqueous uncrosslinked plastisol of being made by methyl methacrylate and methacrylic acid.After gelation, obtain clear films.DE-OS 27.22.752 (

GmbH) plastisol with nucleocapsid structure has been described.Described nuclear is made of the multipolymer of methacrylic acid ester methyl ester, butyl acrylate and butyl methacrylate, and described shell mainly is made of methyl methacrylate.DE-OS 28.812.014 (du Pont) has described the photosensitivity plastisol of being made by methyl methacrylate and methacrylic acid.

DE-OS 29.101.53 (Bayer AG) has described the crosslinked acrylic elastomer that is incorporated in the dispersion.DE-OS 39.00.933 (BASF AG) has described by unsaturated ester, the glycidyl methacrylate of methyl methacrylate, alkyl methacrylate, list or dicarboxylic acid and has comprised the plastisol that the monomer of basic nitrogen group or hydroxyl constitutes.DE-OS 40.300.80 has described the mixture that is made of spray-dired dispersion and spray-dired suspension, described suspension, is made of as the opposing party butyl methacrylate and methyl methacrylate as a side methyl methacrylate and alkyl methacrylate.Can choose wantonly and add the monomer that adheres to promotion property, for example vinyl imidazole.EP 544 201 (Nippon Zeon Co.Ltd) has described by alkyl methacrylate and the diene plastisol mixture that constitutes of divinyl and isoprene for example.Sulphur or ZnO are as optional linking agent.Carry out crosslinked via carboxyl.

Known to PMMA and the floor covering formed as the phthalic acid benzyl monooctyl ester of softening agent from DE 39 03 670 (Pegulan AG).With plastisol mixture heating up to 120 ℃ and further be processed into floor covering immediately.Do not see relevant statement with the plastisol stabilization.

The shortcoming of prior art

Disadvantageously, a large amount of softening agent industrial important and that use always can not be used for the PMMA-plastisol, because the stability of Zhi Bei plastisol is not enough thus in the prior art.At this, important parameters is that the viscosity of the plastisol of product processing difficulties is improved.

Summary of the invention

The proposition of purpose:

The objective of the invention is to, the no chlorine plastisol with favorable mechanical performance and wide work range is provided.Make every effort to constant viscosity during whole processing.In addition, should prevent the plasticizer exudation that adds.Described oozing out causes the unhandsome color change in plastisol surface and damages use properties.

The realization of purpose:

Realized described purpose by the multipolymer of forming by following material:

(1) methyl methacrylate of 39-99 weight % and

(2) ester of the methacrylic acid of 60-0 weight % or vinylformic acid and radical of saturated aliphatic alcohol, wherein said alcohol can have the chain length of 2-6 carbon atom, and described chain also can be a branching, particularly preferably is butyl methacrylate and Propenoic acid, 2-methyl, isobutyl ester at this,

(3) linking agent of 0.05-1 weight % or linking agent mixture, and

(4) count the softening agent of 50-200 weight % based on (1)-total amount/summation of (3).

Can use following material as linking agent:

-alkyl methacrylate

-triallyl cyanurate

-trimethylolpropane trimethacrylate

-ethylene glycol dimethacrylate

-1, the 4-butylene glycol dimethacrylate

-pentaerythritol triallyl ether.

Also can use the mixture of above-mentioned substance.

When using acrylate, the content of acrylate should be adjusted to and make freezing temperature not drop in the practice in significant 60-65 ℃ the Tg limit.

Can use the softening agent of in PVC-technology, using as softening agent, as for example:

Phthalic ester plasticizer, as for example dioctyl phthalate (DOP), diisoheptyl phthalate, phthalic acid two-2-(ethyl hexyl) ester, dimixo-octyl phthalate or diisononyl phthalate,

The ester of aliphatic dicarboxylic acid, as for example adipic acid ester, azelate and sebate,

Phosphoric acid ester, as for example tricresyl phosphate (toluene ester) or tricresyl phosphate-2-(ethyl hexyl) ester or di(2-ethylhexyl)phosphate phenyl isodecyl ester,

The alkyl sulfonic ester of phenol,

Citrate, as for example ethanoyl-tributyl citrate or tributyl citrate,

Trimellitate, as for example tri trimellitate-2-(ethyl hexyl) ester or tri trimellitate isooctyl acrylate,

Epoxidation product, as for example epoxidized fatty acid ester, epoxidized linseed or epoxidized soybean oil,

Polyester plasticizer, as for example by (third-, fourth-, penta-and oneself-) polyester that forms of glycol and dicarboxylic acid.

Softening agent also can be used as form of mixtures and uses.

First and foremost, except the softening agent such as senior polyglycol, phthalic acid polyester or adipate polyester etc. of middle polarity, also can consider low polar softening agent, as the alkyl ester of for example phthalic acid, the alkyl ester of hexanodioic acid, alkyl ester, clorafin, trialkylphosphate, aliphatic series or the araliphatic polyester of sebacic acid.

What can be considered hint is that common all softening agent that PVC is fit to that also can use wherein are stressed that O-phthalic acids softening agent group especially owing to its outstanding industrial significance.

At Kunststoff-Handbuch, the editor is H.K.Felger, the 1/1C volume, people such as Hanser Verlag 1985 and H.F.Mark, Encyclopedia ofPolymer Science and Engineering, augment volume, the 568-647 page or leaf can find the detailed description to the softening agent that is fit among the J.Wiley 1989.The also selection that can obtain suitable softening agent from DE-C 2,543 542.

Can should be mentioned that Di Iso Decyl Phthalate, phthalic acid benzyl monooctyl ester and dioctyl phthalate (DOP) especially.Described in detail as mentioned like that, with the polymer P of per 100 weight parts) consumption of using 40 to 200 weight parts uses softening agent.

Prepare product of the present invention

Product is spray-dired emulsion polymer.Carry out the preparation of spray-dired emulsion polymer according to EP 477 708 and EP 154 189 described exemplary preparation manipulation rules.

In water-hydronic VA still is installed 80 ℃ of following polymerizations.Stirring velocity is 45 rev/mins.In the VA-still of propeller type stirrer is housed in about 1300 rev/mins of following emulsifications.

In order to improve the performance on the special coating technology,, can also add a small amount of polyamino acid amides and/or end capped (verkappten) polyisocyanates as for example adhesivity, hardness, water tolerance and salt fog resistance.

Can also comprise a small amount of following monomer in the polymkeric substance: add unsaturated carboxylic acid, as for example methacrylic acid or vinylformic acid, hydroxyalkyl methacrylate is as for example hydroxyethyl methylacrylate in addition, in addition vinyl cyanide, vinyl imidazole or methacrylic acid-2-dimethylamino ethyl ester.

Decide according to Application Areas, plastisol is used with colored state (for example floor covering) not or with colored state or occupied state (for example chassis protection composition).Under the situation of painted or the composition of filling, the consumption of pigment and filler is generally the as many as 400 of per 100 parts by weight polymer compositions, preferably as many as 200 weight parts.The form of silicon-dioxide, silicate or sand, talcum, clay such as wilkinite, glass powder, aluminum oxide or hydration that at first can consider chalk, also has barite, kaolin, various modification in addition can be considered TiO as filler ₂, ferriferous oxide, carbon black be as pigment.Filler or pigment is the size of particles to be fit to advantageously, and for example the size of particles in the scope of 0.2 to 30 μ m is used (according to Ullmanns

Der techn.Chemie, the 4th edition, the 5th volume, the 725-752 page or leaf is measured).

Can by measurement flow through survey meter (Kratel GmbH,

＂ KratelPartoskop F ＂) the absorbancy of the suspension of particle in water of measuring cell measure particle size distribution.Filler for example can be precipitated and/or grind and optional the coating.

In addition, plastisol can also comprise conventional additive, for example stablizer of dispersing auxiliary, viscosity modifier such as emulsifying agent and organosilicon, heat resistanceheat resistant, light and oxygenizement.Also can be by adding for example plastogel of azo-compound preparation foaming of whipping agent.

Be suitable for characterizing molecular dimension in the nsp/C-value of in chloroform or Nitromethane 99Min., measuring under 20 ℃ (7, the 294 pages of Makromolekulare Chemie, 1952).Described nsp/C-value is usually in the scope of 120-600ml/g.

Favourable effect

Plastisol of the present invention is suitable for whole application, is those of Application Areas as for example pre-determining for PVC-and PAMA-plastisol.

What should emphasize especially is the friction layer (Laufschicht) that is used as floor covering on the given carrier by putting on.In addition, industrial interested be can be by the free-standing transparent film of described plastisol preparation.In addition, also can mention the purposes that is used for wallpaper, plastics awning (LKW-awning), covering for roofs, panel board cover and other etc.The work range of widening of plastisol particularly importantly.

Following table shows multipolymer of the present invention higher viscosity constant after storage

In all embodiment, all use di(2-ethylhexyl)phosphate phenyl isodecyl ester and tributyl citrate with ratio as the mixture of 2:1 to 1:2 as softening agent.

Described embodiment obviously shows the favourable influence of application linking agent to the stability in storage of plastisol of the present invention.Uncrosslinked plastisol shows that rapid viscosity improves, and this makes further workability become problem, and the raising of the viscosity of crosslinked plastisol remains in the limit.The workability of Zhi Bei plastisol is always better after 4 hours like this.

The viscosity of multipolymer of the present invention should be 10 after 4 hours, 000-20, and in the scope between the 000mPas, preferably 15,000-15 is in the scope of 000mPas.Do not find out described plasticizer exudation.

Claims (3)

1. the plastisol that constitutes by multipolymer, described multipolymer is made up of following material:

(A) methyl methacrylate of (1) 39-99 weight % and

(2) ester of the methacrylic acid of 60-0 weight % and radical of saturated aliphatic alcohol, wherein said alcohol can have the chain length of 2-6 carbon atom,

(3) linking agent of 0.1-1 weight % or linking agent mixture, and

(B) (4) count the softening agent of 50-200 weight % based on (the 1)-total amount of (3).

2. according to the plastisol of claim 1, it is characterized in that using following material as the linking agent in the used multipolymer:

1, the mixture of 4-butylene glycol dimethacrylate or glycol dimethacrylate or (methyl) allyl acrylate or triallyl cyanurate or trimethylolpropane trimethacrylate or pentaerythritol triallyl ether or ethylene glycol dimethacrylate or the above-mentioned material of enumerating.

3. be used to prepare the purposes of floor covering according to the multipolymer of claim 1.