DE2458887A1 - WATER-FILLED OR EXPANDED POLYMER MATERIALS AND METHOD FOR MANUFACTURING THE SAME - Google Patents

Description

PATE NTANV / ALTS OFFICE I IEDTKE - DÜHLING - IXlfcNE

TEL. (089) 53 96 53-56 TELEX: 524 845 lipat CABLE ADDRESS: Germanlapaient Müi.ciien

8000 Munich 2

Bavariaring 4 P.O. Box 20 2403

case Y 26654 - B 63 ^ 7 December 12, 1974

IMPERIAL CHEMICAL INDUSTRIES LIMITED London, United Kingdom

Polymer materials filled or expanded with water and methods of making the same

The invention relates to water-filled or -expanded polymer materials and a method for Manufacture of the same. In particular, according to the invention, there is a selection of certain surfactants taken as emulsifiers for stabilizing the emulsions used to form such materials.

Water-filled or -expanded polymer materials have a cellular structure made of polymer material, which at least initially with water or other aqueous liquids is filled. They are made by emulsifying water with a polymerizable, water-immiscible one Liquid forming an inverse emulsion

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Ranit rMiinnherrt loo. 51/61 070 Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670 43-βΜ

(ie an emulsion in which the aqueous phase is dispersed in the organic phase; sometimes such emulsions are referred to as "water in oil emulsions") and subsequent polymerization of the continuous phase while maintaining the dispersed aqueous phase. The dispersed water droplets thus determine the cellular nature of the material * and the size of the droplets is decisive for the fineness of the cell structure produced. For most applications, the water after completion of polymerization is removed, and to ^n, the term "water-filled or -expandiertes polymer material means in the context of this description in the above manner produced cell-like polymer material, regardless of whether the cell-forming water was removed or not.

Numerous aqueous liquids have already been described for the disperse phase of the "water in oil emulsions", which include water and aqueous solutions with at least 40 % water, the dissolved fractions and admixed water-miscible liquids being lower alcohols, formamides, carbohydrates and inorganic ones Include salts. In a similar way, the terms "water-expanded polymer materials ^B and" water in oil emulsion ¹¹ in the context of the present description are intended to include aqueous liquids containing dissolved or admixed substances where a sol «

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rather incorporation of water-soluble or water-miscible substances may be desirable, such as, for example, the addition of water-soluble free ones described below Acids.

To form. water-expanded polymer materials with an expansion or stretching of · at least 65% _t ie materials which are formed from emulsions containing at least 65 wt.% of dispersed water, it is essential in most polymerizable liquids that are used "permanent" emulsifiers, which are able to maintain the stability of the emulsion at least over the duration of the polymerization reaction (expediently 1 hour) and to keep the water as the disperse phase during the polymerization reaction until the continuous phase is sufficiently solidified that it retains its shape - despite the change in the composition of the mixture during the polymerization. If stability is not maintained during the polymerization, either "collapse" of the emulsion with partial or complete separation into two separate phases or layers or inversion of the emulsion to an "oil in water emulsion" with formation of a latex instead of cellular material. The present invention is only concerned with materials made using "permanent" emulsifiers as described above (which in fact are used for the

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Generation of any water expanded polymeric materials with an elongation of at least 65 % are fundamental). Methods which use surfactants other than the "permanent emulsifiers" above as the sole means of stabilizing the emulsion do not form part of the present invention.

The droplet size that can be achieved in the emulsion depends on the effectiveness of the emulsifier. By using an effective emulsifier, smaller droplet sizes and thus finer cell structures can be obtained, also depending on other factors such as stirring. In the case of such materials, mean cell diameters can be less than 10 μm and, with particularly effective emulsifiers, even submicron size. However, the particularly effective emulsifiers used for the formation of highly expanded materials have so far always led to essentially closed cell structures. The use of an ineffective or inefficient emulsifier or the initiation of destabilization of the emulsion prior to polymerization have previously been proposed, but this leads to a low expansion, ie of less than 65 wt. #. A way has now been found how an essentially open pore structure can be achieved with an expansion of at least 65 % .

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According to one aspect of the invention, a water-filled or -expanded polymer material with an expansion of at least 65 % and a value on the VET scale (see definition below) of at least 10 % is provided.

For the classification of cell structures by polymerization a test was developed for the continuous phase of an inverse emulsion produced polymer materials which is easy to perform and provides reproducible results that correlate well with the photomicrograph Show evidence. To carry out the test, 400 g of a mixture of water and polymerizable liquid are used emulsified into an inverse emulsion using a suitable emulsifier dissolved therein. A polymerization initiator is added and the emulsion is converted into a cylindrical shape with a diameter of 6 cm and the continuous phase then polymerizes. After completion of the polymerization reaction, the resulting transferring the cylindrical block into a funnel with a cylindrical section of the same diameter as the mold, which fits tightly around the block and the funnel is then connected to a vacuum pump which is able to reduce the pressure to a value of about 22 torr over a period of 5 minutes. By weighing the Product before and after the application of pressure, the weight of the water dispensed is determined and expressed as a percentage of the

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originally expressed water weight. This test, which is referred to as the "vacuum drainage test ⁿ " in the context of the description, provides a scale (the so-called "VET scale") ranging from about 80 % (although higher values approaching 100% are theoretically possible) to almost goes to zero.

Most of the products were found to give a value on the VET scale that was either in the range of zero to 5 % or 10 to 80 % . All photomicrographs of materials with values within the range of zero to 5 % showed a majority of closed cells. All photomicrographs of materials with values within the range of 10 to 80 % (VET scale) showed a majority of open cells. However, the latter group of materials can still be subdivided: Most of the materials gave values of 30-80 % on the VET scale and showed only slight changes in the appearance of the photomicrographs and all materials clearly had a very open cell structure. In the range from 10 to 30 % (VET scale) there was a minority of materials whose structures were clearly open-celled according to the microphotographs, but the cell connection holes were visibly reduced, especially at the lower end of the scale. In most respects, these structures or materials behaved like open cells.

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structures, however, for consistency in terms of the ^{properties associated with the "openness 1} ^ of the cell structure, materials are preferred which have values of at least 30 % on the VET scale.

Pre-dried materials can also be checked for their VET value by looking at the material soaks or brings in water until the full amount of water is absorbed and then a sample of appropriate dimensions, as before, subject to reduced pressure. With closed cell materials, it is often difficult to reintroduce the full amount of water, however, in In this relationship, the alternating use of low and high pressures when soaking with water is helpful. But even if the full theoretical amount was not consumed, the corresponded in this way treated materials fairly experienced water loss well with the true VET provided that it is expressed as a percentage of the theoretical amount of water became. The latter, can be obtained from the difference between the density and the density of the same polymeric material of non-cellular nature can be determined.

In order to fully utilize the aqueous liquid as a filling or expansion material, a filling or expansion of the material by or by at least 75 % is preferred.

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The material is expediently an addition polymer, that by polymerizing a liquid monomer on a polymerizable ethylenically unsaturated group therein is formed.

According to a further aspect of the invention, a method for producing a water-filled or expanded polymer material with an elongation of at least 65 % and a VET value of at least 10 % is provided, in which a mixture containing at least 65% by weight of an aqueous liquid , a polymerizable water-immiscible liquid and an emulsifier is emulsified to form an inverse emulsion, after which the continuous phase of the emulsion is polymerized using a monomer-soluble initiator, the emulsifier being an "amphipathic" material (with mutual affinities) which is a component solvated by the polymerizable water-immiscible liquid and another component solvated by the aqueous liquid, the component solvated by the polymerizable, water-immiscible liquid having a negligible reaction with the polymerizing agent Mixture shows and is incompatible with the polymer formed.

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About polymerizable, water-immiscible liquids which are intended for use within the scope of the inventive Process suitable include ethylenically unsaturated monomers such as acrylic and methacrylic esters and nitriles, vinyl esters, vinyl aromatics and vinylidene and vinyl chlorides, the latter the formation and polymerization of the emulsion at elevated pressures (to liquefy the otherwise gaseous monomers) require.

Whether open or closed during the polymerization reaction Cells are formed, depends largely on the nature of the emulsifier components produced by the polymerizable liquid are solvated and in particular whether these components have a negligible reaction with the polymerizing Show mixture and / or are compatible with the polymers formed. These. Components can be related to their reactivity towards the polymerizing reaction mixture can be divided into three groups:

(A) those which copolymerize with the polymerizable liquid during polymerization;

(B) those which are completely inert during the polymerization or to the polymerizable liquid not reactive and

(C) those that occur during the polymerization, for example

enter into a limited response by grafting.

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Other factors (related to the above can), which can have an influence on whether an open or closed cell structure is formed or not, are determined by the choice of initiator, the nature of the polymerizable liquid and the concentration of the Emulsifier formed.

Components of type (A) always result in closed cell structures, regardless of the choice of initiator or the polymerizable liquid, provided that it is with the polymerizable liquid of the continuous Copolymerize phase. Components of type (B) always result in open cell structures, provided that no large Excess of emulsifier is present. Type (C) components are of intermediate reactivity-between types (A) and (B) - and can be used to create open or closed cell structures, depending on the combined Function of their reactivity and concentration to form.

With type (C) the reactivity results from the presence of mobile hydrogen atoms in the molecule, typically derived from methylene groups adjacent to isolated double bonds or from hydrogen atoms on tertiary carbon atoms.

The activity of these components can be published from

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clear data (e.g. Rushman & Simpson, Paint Research Station, Research Memorandum No. 217) on the CX-methylenic Activity of individual component aortas can be predicted.

For example, typical fatty acid methyl esters have the following O (^ methylenic activities (Kr):

Kr

Palmitate (saturated C ₁₆ ) O oleate (monoethenoid C ₁₈ ) 0.081 9:12 linoleate (dlethanoid C ₁₈ ) 0.605

9:12:15 Linolenat _{Λ 1n}

(tri-ethenoid C ₁₈ ) ^Ί ' ^υ

When these fatty acid esters or derivatives with equivalent carbon chains are used for the preparation of emulsifiers, the relative reactivities of these chains are obtained by comparing their Kr values. If mixtures of such chains are used, as can be found, for example, in natural oils, the total activity of the mixture can be determined by adding the contributions of the individual chains, based on their percentage by weight in the mixture. For example, for a natural oil with 50% by weight of a monoethenoid C ^ ester, the activity contribution of this ester is 50 % of 0.081, ie 0.041. In order to explain

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Based on these factors, the total activities of linseed oil and tall oil are calculated below:

- saturated % Activity
contribution linseed oil monoethenoid 10 0 diethenoid ■ 22 0.018 triethenoid 16 , 0.097 Total activity 52 0.572 - saturated 0.687 Tall oil monoethenoid 8th 0 diethenoid 46 0.037 1 triethenoid 41 0.248 Total activity 3 0.033 0.318

When the total ot-methylenic activity of the emulsifier is formed by linseed oil or tall oil (such as the alkyd emulsifiers described below) the calculated total activity of the oil the o <-methylenic Activity of the emulsifier. The calculated activities indicate whether an emulsifier molecule interacts with the polymerizing Reaction mixture is likely to react or not. To get a statement about the probable extent

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an "activity index" can be derived from the reaction between the emulsifier and the polymerizing reaction mixture (as the product of the cx-methylenic activity of the emulsifier and its concentration in percent by weight of the polymerizable liquid). It has been found that with most polymerizable liquids (e.g. acrylic acid and methacrylic acid esters) a negligible reaction between the emulsifier and the polymerizing reaction mixture will only take place if the activity index is less than 0.13 when using hydrogen-removing initiators. Thus, for example, the maximum amount of linseed oil and tall oil, which can be used when the polymer material should have a major proportion of open cells at 0.19 or 0.41 wt.% Of the polymerizable liquid (ie, 0.13 / 0.687 or 0.13 / 0.318). These are of course only the weights of the oils and not the weights of the entire emulsifier.

In the case of polymerizable liquids that enter into grafting reactions particularly easily, such as styrene an activity index of less than 0.13 may be necessary for open cell generation. Indeed it can it when the graftability of the polymerizable liquid becomes too high, even it will be necessary that the activity index becomes zero, i.e. a type B emulsifier is used will.

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While it may be necessary for open cell production to limit the activity index in this manner when using hydrogen scavenging initiators, such limitation is unnecessary when a non-hydrogen scavenging initiator is used. In such cases, emulsifiers of type C behave like those of type B. Examples of hydrogen-removing initiators include peroxides, hydroperoxides, peresters, monomer-soluble redox systems such as peroxides activated by transition metal ions and by electromagnetic radiation such as δ ¹ ", UV- and visible radiation induced radicals Examples of initiators that do not cause hydrogen-scavenging grafting reactions include azo initiators such as azobisisobutyronitrile and 2,2-azobisvaleronitrile.

During the polymerization, polymer molecules grow within the polymerizable liquid. The component the emulsifier produced by the polymerizable liquid is solvated is also located within the polymerizable liquid. When the growing polymer and that which can be solvated by the polymerizable liquid Component are compatible, these two are at all concentrations of the polymer within the polymerizable Liquid coexist. When the polymer and the component solvatable by the polymerizable liquid the emulsifier, on the other hand, are incompatible, the emulsifier becomes

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rejected by the polymer with the formation of a differentiated phase. Whether or not the component of the emulsifier which can be solvated in the polymerizable liquid is incompatible with the polymer can be determined for the purposes of the invention by an observation whether the partially or completely polymerized liquid having at a content of 10 wt.% of her solvatable component of the emulsifier at the polymerization temperature in the absence of cell-forming aqueous liquid more than one phase. the presence of a plurality of phases can be detected turbidimetrically or by turbidity measurement when a difference in the Refractive index exists between the phases. If there is no such difference, the majority of phases can be indicated by the presence of multiple glass transition temperatures. These and other techniques for detecting the different phases are described by Sonja Krause in J. Ma cromol. May be. 2 (2), (1972) 251-314, reviews in Macromol. Chem., Described. Although the component solvated in the polymerizable liquid is not normally present in such high proportions, it is preferred to use such a proportion of 10% by weight of the polymerizable liquid in the examination of the incompatibility in order to increase the sensitivity of the test.

In accordance with common commercial practice, the minimum

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The amount of emulsifier used is such that it gives the desired results, since any excess is a waste of starting material which reduces the efficiency of the process. It is assumed here that such common practice is followed in the practice of the invention. The minimum amount is specific for each material batch and the special conditions, but fortunately it can be conveniently determined experimentally for each individual case. If sufficient excess amounts of emulsifier are used, the "openness ^{11 of} the cell structure can be lost in most cases" even with emulsifiers of the type B above.

A certain guidelines can be given in general terms: Thus, although as little as 0.02% by weight of emulsifier of the polymerizable liquid to stabilize an emulsion with 80 wt% water in methyl methacrylate at application more effective stabilizers described in the following examples.. may be sufficient, higher emulsifier proportions may be required to maintain higher water contents in a disperse state and when using the less effective emulsifiers that are described there. Even type B emulsifiers tend to form closed cell structures when used in proportions much greater than 5 % . However, emulsifier levels of less than 1 % are generally sufficient for most emulsifiers.

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Levels below 0.5% are generally sufficient with the more effective emulsifiers and generally produce structures with a majority of open cells, except for "some emulsifiers with high cX-methylenic activity when used in conjunction with a hydrogen scavenging initiator. The applicant's The preferred range of emulsifier proportions is therefore 0.02 to 5 % and in particular less than 1 % and especially less than 0.5 % if the emulsifier is sufficiently effective, all emulsifier proportions being expressed as percentages by weight of the polymerizable liquid and all upper limits are subject to the overriding factors described above, which affect each individual situation, if open cell structures are required.

It has been found that amphipathic materials that meet the global demand for permanent emulsifiers, Generally solvatable components require »which are large in comparison to the solvating molecules and are of a chain-like structure. This applies to both the aqueous liquid and the solvated by the polymerizable liquid Components. For example, small hydrophilic groups such as isolated hydroxyl or carbonyl groups are for alone is insufficient as the only water-solvatable Component of an emulsifier if high water contents are required, while the long chains of a water-

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- IO - ·

soluble oxyethylated polyols such as polyethylene glycol can be extremely effective. The chain-like solvatable components can be straight-chain or branched be.

More specifically, the component solvatable by the aqueous liquid can be any chain-like component Component having a molecular weight of at least that is soluble in the aqueous liquid. Examples of suitable chain-like components include:

water-soluble oxyethylated polyols such as polyethylene oxide condensates with hydroxyl or methoxylated ends;

Polymers of vinyl pyrollidone and copolymers thereof;

Dimethylaminoethyl methacrylate or diethylaminoethyl methacrylate - e.g. as hydrochloride-containing polymers;

Methacrylamide or acrylamide containing polymers;

Polymers that contain substantial amounts of carboxyl groups, such as polymers containing methacrylic acid, Acrylic acid or itaconic acid either as free acid or solubilized by a change in pH, i.e. Formation of the sodium, potassium, ammonium or organic

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ganic amine salt, contain;

Copolymers of ethylene oxide, with minor amounts ¹ of other alkylene or alicyclic oxides;

Polyvinyl methyl ether;
Polyethylene amine;

natural polymers such as hydroxyethyl cellulose, starch or carboxymethyl cellulose;

Polymers that contain substantial amounts of hydroxyl groups, such as hydroxyethyl or isopropyl methacrylate containing polymers and hydrolyzed polyvinyl acetate.

For the generation of open cell structures, the liquid should be solvatable by the polymerizable liquid Component has a negligible reaction with the polymerizing component Possess reaction mixture and be incompatible with the polymer formed, in addition to the solvatability required by it as an anchoring group of the emulsifier. Of course, the choice depends therefore very much on the polymerizable liquid used. According to a general guide however, the long-chain molecules can be used as the component that can be solvated in the polymerizable liquid can be built into an emulsifier, divided into two groups according to the following guidelines:

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Appropriate chain-like components created by monomers such as acrylic and methacrylic esters as well as vinyl aromatic monomers that are solvatable include:

Polymers of long-chain esters of unsaturated acids such as stearyl, lauryl, acetyl, 2-ethylhexyl, Hexyl and butyl esters of acrylic and methacrylic acids;

Polymers of vinyl esters of long chain acids such as vinyl stearate and vinyl ester of versatic acid;

"Self-polyesters of hydroxy fatty acids such as e.g. 12-hydroxystearic acid, fatty acids from hydrogenated castor oil and the hydroxy acids of carnauba waxj

polymeric vinyl alkyl ethers or higher alkylene oxides such as polypropylene oxide of molecular weight from 1000-3000;

aromatic branched and linear polyesters such as monobasic acid modified alkyd resins, including of urethane alkyd resins;

aromatic polyethers;

Polymers of styrene, vinyl toluene and tertiary butyl styrene.

For matching chain-like components that go through more polar monomers such as ethoxyethyl methacrylate, methyl methacrylate, Ethyl acrylate, butyl acrylate, acrylonitrile solva-

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can be controlled include:

Polymers of esters of short-chain alcohols and unsaturated acids such as methyl methacrylate, Butyl acrylate, ethyl acrylate, polyester of short chain Acids and alcohols.

Most of the above polymerizable liquid solvatable components are compatible with those of the Polymers derived from special monomers are incompatible, provided that the molecular weights are sufficiently high except when the polymers and components are identical. However, if the emulsifier has several types of The above chain-like molecules are introduced as components which can be solvated in the polymerizable liquid it is not essential since / 3 has any component the polymerizing mixture is incompatible, provided that the global comparison indicates an incompatibility results, so that the necessary rejection of the emulsifier is given during the reaction. Mixtures of components from both groups are provided in a common emulsifier molecule, provided that that the global comparison ensures sufficient solvation of the Emulsifier as a whole results.

The selected components can be combined in different ways to achieve a variety of

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different types of emulsifiers. To suitable types of emulsifiers include (1) simple block or alternating block copolymers, (2) amphipathic copolymers with chains hanging from a "backbone", the latter preferably being evenly spaced along the backbone and (3) arbitrary condensation products from polyfunctional acids, polyfunctional Alcohols and water-soluble oxyethylated polyols. These individual types will now be considered in order.

Suitable simple block or alternating block copolymers comprise blocks of water-solvatable chain-like components and in polymerizable liquid solvatable chain-like components, where the molecular weight of each component is at least 400 and the HLB value of the copolymer is less than 9, the components that can be solvated by the polymerizable liquid have a negligible reaction with the polymerizing components Possess mixture and are incompatible with the polymer formed, as described herein.

Suitable copolymers of type 2 above include amphipathic molecules which are polymerizable by the Liquid solvatable chain-like "backbone" as well as a large number of chain-like ones hanging from the backbone

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Have components that can be solvated by the aqueous liquid and the molecular weights of at least 400, the copolymer having an HLB of less than 12 and preferably less than 9. The molecular weight The backbone is of course determined by the number and molecular weights of the attached components and also determined by the HLB value. The HLB value becomes convenient during the preparation of the copolymer by suitable means Adjustment of the weight ratio of the backbone to the adherent solvatable by the aqueous liquid Components adjusted or set. For the production of open-cell material according to the invention must the "backbone" has a negligible reaction with the polymerizing Have mixture and be incompatible with the polymer formed if the backbone is the only one component solvatable by the polymerizable liquid is.

A variant of the above emulsifiers has a plurality of chain-like components suspended from the backbone and solvatable by the polymerizable liquid having a molecular weight of at least 400 in addition to those solvatable by the aqueous liquid attached components. In the case of molecules with attached components, the polymerizable liquid are solvatable, it is not essential that both the backbone and the polymerizable fluid

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solvatable pendant components are incompatible with the polymer formed, provided that that the ratio of the incompatible to the compatible components is at least 1. However, it is preferred that at least the pendant in the polymerizable liquid solvatable components with the polymerizing mixture are incompatible.

In appropriate cases, the molecules can be grafted on by pendant chain-like components a preformed polymer molecule can be generated. Alternatively, the chain-like components, the pendent Components should form, be provided with a reactive group with the monomer of the polymer backbone is copolymerizable; by the polymerization of such monomers in the presence of such components, the reactive groups built into the backbone, whereby the components are attached as pendent chains. Addicted Of the nature of the backbone desired, the reactive groups can be separated by any suitable mechanism, such as condensation or vinyl polymerization, be copolymerizable. So For example, to illustrate these relationships using a simple two-component example, polyethylene glycols having glycidyl methacrylate ends are copolymerized with methyl methacrylate to form a molecule in which the polyethylene glycol chains on a polymethyl methacrylate backbone hang.

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Emulsifiers of the third type can be prepared by reacting the three components (with any other components such as monofunctional acids and alcohols as chain ends) in stages or in a single reaction will. For example, the polyols and polyacids are converted to a polyester, which is then reacted with the oxyethylated polyol components will. It has been found, however, that by copolymerizing all of the above ingredients in a single reaction particularly effective emulsifiers can be obtained.

The emulsifiers preferred by the applicant are alkyd resins, which are produced by reaction products of a polyol with a functionality above 2, a water-soluble oxyethylated polyol, a polybasic acid or their anhydride and a monobasic acid with a carbon chain of at least 5 carbon atoms and which, as explained above, only have a negligible reaction, if at all of the polymerizing reaction mixture and their stabilizing solvated by the polymerizable liquid Groups (i.e. groups different from the oxyethylated polyol) with the during the polymerization of the continuous phase formed polymer material are incompatible.

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It has been found that the more branched an alkyd is, the more effective it is as an emulsifier. The extent The branching can be achieved through the selection of polyols and polyacids can be controlled in the preparation of the alkyd. As a general guide, the simple relationship of Kahn (J. Polymer Science 4 £ (1961) 152) can be used, by which a theoretical critical gel point is defined. One has the following equation:

-1 ^p OH ^p A

where P ₀ J _{1 is} the probability that an OH group will react; p _{A is} the probability that an acid group will react;

f 'containing the average functionality of the hydroxyl groups Molecules is and

g 'containing the average functionality of the acid groups Molecules is.

A preferred alkyd emulsifier is one that has a gelling structure that occurs when the product Pq _H P ^ is 1 or less than 1.

Suitable polyols include glycerine and pentaerythritol, the latter being used to achieve a highly branched one Alkyds is particularly useful. Equimolar Mi

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Mixtures of pentaerythritol and glycerine are particularly suitable.

The water-soluble oxyethylated polyol. is preferably a polyethylene glycol. These are usually available as chains with hydroxyl ends and through the condensation of these hydroxyl end groups, these molecules take part in the alkyd formation. However, they can be introduced into the reaction mixture in other forms which allow the hydroxyl groups to arise in the reaction mixture, for example in the form of a hydrolysable ester. The most suitable molecular weights of the water-soluble oxyethylated polyol be within the range of 200 to 2000 and preferably in the range of 400 to 1000. The amount of oxyäthyliertem ₃ polyol is present in the alkyd is most suitably within the range of 10 to 60 wt. % of the alkyd, preferably within the range of 20 to 60 %.

The polybasic acid or its anhydride can, for example by an aliphatic dibasic acid such as adipic acid or an aromatic dibasic acid such as Phthalic acid, however, acids with higher basicities, such as trimellitic acid, are because of them produced stronger branching preferentially. Mixtures of polybasic acids or their anhydrides can be used

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will. The amount of polybasic acid required depends on the amounts of polyols and oxyethylated ones used Polyols, as they condense with them to form an alkyd according to the degree of branching.

Preferably, the monocarboxylic acid is a Cc _-1 O? "Carboxylic acid having a straight or branched chain. It may suitably a natural fatty acid (which generally have mixtures of C _<j2.i8" are formed based be ^{Cartooilsäuren s} ^ ⁿ ^ or by it, oils .

The acid number of the alkyd is determined by the degree of conversion in the alkyd formation reaction and by the relative proportions of originally present acid and hydroxyl groups dominated. Alkyd resins with Acid numbers in the range from 5 to 30 mg KOH / g are preferred.

It has been found that the emulsion can be glatter.erhalten by the addition of a small proportion, such as from 0.5 to 5 wt.% Of the polymerizable liquid and preferably about 1.5 wt.% Of a free acid such as methacrylic acid, hydrochloric acid, oleic acid or acetic acid , the acids having a reducing effect on the viscosity of the emulsion. Such small amounts of acid have no noticeable effect on the stability of the emulsion, if

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- 29 this is shown once formed.

To avoid resistance to the opening of the cells during the formation of the cellular material the polymerization reaction is preferably at a temperature above the glass transition temperature of the emulsifier component, which is solvated by the polymerizable liquid.

The water-expanded polymeric materials according to the invention and the process for their preparation can can be used for most of the applications where water expanded polymers are already known. she however, are particularly beneficial where the water is to be removed and where the open cell structure is for other reasons is required. Thermoplastic water-expanded polymers can be provided with a non-cellular skin, by allowing heat and pressure to act on the object (for example as described in GB-PS 1,360,397 is) and translucent or transparent fields can also be used in sheet materials of the cellular material formed by melting selected areas (for example, as described in U.S. Patent 3,832,428 is described). For example, the skin can have a permanent and very attractive surface finish a sheet of material for kitchen work surfaces, kitchen

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Cabinet doors, exterior doors, bathroom tiles, coffee tables or Boards and other applications offer where a consistently smooth or textured surface is desired. the Translucent fields can be created, for example, to provide an external door with a visual effect or to serve as a useful puncture in a showcase or for illuminated advertising. These melting processes are However, only possible when the dispersed water has been removed and the present method according to which a material with a major part of open cells is obtained, allow a much faster and cheap one Removal of water.

It is a feature of the emulsifiers described here that they have a negligible reaction with the polymerizing agent Result in a mixture and they will not cross-link the polymer molecules themselves. Thermoplastic materials such as polymethyl methacrylate, which are not crosslinked in any other way, thus lose their thermoplasticity not and their ability to comfortably form said skin and / or clear panels. Other advantages arise when the cabinet doors, table tops and other objects are to be transported, thereby, that by removing the large proportions of dispersed water the weight of the slabs or slabs being transported other objects is very significantly reduced.

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The polymer materials can also be used as filtration membranes, taking advantage of the openness of their cell structures to be used. By appropriately selecting rigid or flexible materials, they can also help in manufacturing of bandages, upholstered furniture or goods or for the formation of molds for slip casting will.

The invention is explained below with the aid of examples.

Examples 1 to 6

0.4% by weight of emulsifier and 1.5% by weight of methacrylic acid (based on the weight of the methyl methacrylate) were dissolved in methyl methacrylate as the polymerizable liquid. To 250 g of the resulting solution were added 750 g of water at 55 ⁰ C, the mixture was suspended with a 27 mm (diameter) "poppy head" stirrer (turbine mixer) to form a "water in oil emulsion" shear forces. The water was added steadily over a period of about 10 seconds and the shear rate was kept low by rotating the mixer at about 800 to 900 rpm. It has been found that much higher shear rates result in inversion of the emulsion to an oil in water type.

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The emulsion produced was divided into two portions, the first to test the stability of the emulsion used depending on the time. The emulsion was visually inspected immediately after it was formed and then left under ambient conditions for 20 hours, after which it was tested again.

To the other portion was added 1.5 wt.% T-Butylperpivolat added and the mixture into round PoIythenformen of 10.7 cm diameter and 6.4 cm depth poured. It was then placed in an oven at 50 ^° C. for about 4 hours to polymerize the methyl methacrylate. After this time, the forms were taken out of the oven and their contents checked. The samples with the water remaining in a dispersed state formed stiff, smooth-surfaced blocks with water dispersed therein. In this test, emulsions that are not effectively stabilized form solid materials in various shapes and forms, all of which deviate from the shape of the mold and thus give an indication of different degrees of separation of the phases.

The blocks produced were then placed for drying in an oven at 13O ⁰ C. All appeared to have similar drying rates.

509825/0382

example 1

The alkyd resin was made by condensation of pentaerythritol, polyethylene glycol 600 (i.e. polyethylene glycol with a nominal molecular weight of 600), trimellitic anhydride and tall oil in molar ratios of 0.6 / 2.1 / 1.2 / 3 produced. The resulting alkyd had an acid number of 19 mg KOH / g, a viscosity of about 2 poise and a PÄG (i.e. polyethylene glycol content) of 54

The first serving quickly showed a small amount of secretion, However, it was only partially separated after 20 hours. The polymerized portion gave a good block that showed that the emulsion was maintained during the polymerization. -

Example 2

The alkyd was obtained by condensation of pentaerythritol, polyethylene glycol of nominal molecular weight of 600, but which was believed to be greater than that of Example 1, trimellitic anhydride and tall oil in mole ratios of 0.6 / 2.1 / 1.2 / 3. The resulting alkyd had an acid number of 8.2 mg KOH / g, a viscosity of 12 poise and one PÄG of 54 wt. #.

. 509825/0962

No separation of the emulsion was observed at the beginning. Even after 20 hours there was no separation, however, the structure seemed coarser than at the beginning. Again, the polymerized block was well defined. The prepolymerized emulsion appeared to be more stable than the previous example and it passed noticeable difference in the appearance of the blocks, of which those of the previous example have a coarser structure had and were more crumbly.

Example 3

The alkyd was prepared by condensing pentaerythritol, polyethylene glycol 600, trimellitic anhydride and tall oil in molar ratios of 0.6 / 3.8 / 2.33 / 3.0. The resulting alkyd had an acid number of 21.7 mg KOH / g, a viscosity of 35 poise and a PAE of 65 % by weight.

There was no visible separation of the emulsion at the beginning, but a partial separation was evident 20 hours. However, the emulsion polymerized to produce a well-defined block.

Example 4

The alkyd resin was made by condensation of pentaerythritol, glycerine, polyethylene glycol 600, trimellitic acid

509825/0962

. - 35 - ■

anhydride and tall oil in mole ratios of 0.6 / 0.6 / 1.2 / 1.2 / 3. The resulting alkyd had a Acid number of 17 mg KOH / g, a viscosity of 10 poise and a PÄG of 39 wt. #.

There was no separation of the emulsion at any time during the 20 hour test and the emulsion seemed to have a fine structure throughout. The block formed was well defined with smooth surfaces.

Example 5

The alkyd resin was obtained by condensation of pentaerythritol, Glycerine, polyethylene glycol 600, trimellitic anhydride and tall oil in molar ratios of 0.6 / 0.6 / 1.2 / 1.2 / 3 manufactured. The resulting alkyd resin had an acid number of 17 mg KOH / g, a viscosity of 13 poise and a PÄG of 40 Gew.jtf.

No visible separation of the emulsion was observed at any time during the 20 hours of testing. The emulsion polymerized into a well-defined block with a smooth surface, which is indicative of the effectiveness of this alkyd speaks as an emulsifier under these conditions.

509825/0 982

Example 6

The alkyd resin was made by condensation of pentaerythritol, glycerine, polyethylene glycol 600, trimellitic anhydride and soybean fatty acid in mole ratios of 0.6 / 0.6 / 1.2 / 1.2 / 3. The resulting alkyd resin had an acid number of 21 mg KOH / g, a viscosity of 13 poise and a PÄG of 40 Gew.itf. This alkyd was im essentially similar to that of the previous example, only that tall oil had been replaced by soybean fatty acid.

No emulsion separation was observed even after 20 hours, but the emulsion appeared thinner and to be coarser than that of the previous example. Again, the block was well defined and had a general appearance like that of the previous example.

The polymer materials of Examples 1 to 5 all had VET values greater than 30% and the material of Example 6 had a VET value greater than 20 %.

Example 7

An emulsion was made using the mixture of Example 5 prepared except that the weight ratio of

509825/0962

1 has been changed and increases the Alkydkonzentration to 2 wt% of methyl methacrylate to 9 water.. While the "poppy seed" mixer was used in the initial stages of water addition to form the emulsion, a peristaltic pump was used with the water dropwise added when the emulsion became particularly thick, ie after about 80 % of the water had been added. In this way a stable emulsion was produced which was successfully polymerized and the water was again smoothly removed. The material had a VET value greater than 30 %.

Example 8

The drying rates of water-filled ones made using the present alkyd resins as emulsifiers expanded polymers were compared to those of polymers made using other Emulsifiers were produced. It has been found that the blocks of the previous examples with approximately the same Speed appeared to be drying with that of Example 4 being considered typical. From the emulsifiers, previously used by the applicant did not appear to show any significant difference in drying rates with monomer-soluble ethyl cellulose being considered typical.

509825/0962

Two emulsions (A and B) were prepared accordingly, A being prepared as described in Example 4 and B being identical except that no methacrylic acid was added and the alkyd was replaced by 2% ethyl cellulose (Hercules N-10). The emulsions were cm in separate, suitable for the production of cabinet door panels forms of χ 91 91 up to a depth of 6.4 cm filled and then cured in an oven at 5O ⁰ C "".

The molds were removed from the oven and brought away the blocks formed therefrom and held at 130 ⁰ C drying oven. Block A was found to be dry after about 2.5 days, while Block B took a full 10 days to reach the same condition. This confirmed the impression obtained earlier on the basis of the smaller blocks of the preceding examples that the water is given off noticeably more quickly with the materials according to the invention.

Example 9

Further dry runs were carried out using emulsions A and B from the previous example. These emulsions were poured into cylindrical molds of the type used in Examples 1-6. The blocks were placed in an evacuated room at room temperature and weighed at intervals. It was found that

509825/0962

the blocks produced from emulsion A in the presence of alkyd emulsion stabilizers lost 50 % of their water after about 30 seconds and 65 % after about 5 minutes * while the blocks produced from emulsion B using ethyl cellulose did not change their weight noticeably.

The blocks A and B were later immersed or soaked in water and the water loss was determined under the conditions of the VET test. Block A returned a value greater than 30 % on the VET scale, while the value for block B was less than 5 % .

Examples 10 to 20

These examples represent series tests that demonstrate the effect of concentration when using alkyd resins with different "unsaturation" of the monobasic acid component should show, d. H. there have been alkyd resins with different degrees of reactivity to that used Monomers used. Three alkyd resins were investigated, each formed by the reaction product of pentaerythritol, Glycerin, polyethylene glycol 600, trimellitic anhydride and a monobasic acid in molar ratios of 1/1/2/2/5 (acid number: 15.7 mg KOH / g), 1/1/2/2/5 (acid number: 18 mg KOH / g) and 1.25 / 1.25 / 1, 5/2/5 (acid number: 27.6 mg KOH / g) were formed, the three alkyd resins being monobasic acids

509825/0 9 62

of linseed oil or tall oil or capric acid. In In Table I given below, the alkyd resins are identified by their monobasic acids. In all Cases the emulsion had the following components:

Methyl methacrylate 80 parts by weight

Stabilizer - (different:

see table i)

demineralized, _{pn r + iii1ii}

Water (pH 7.3) ^{320 parts by weight}

Benzoyl peroxide initiator 1.6 parts by weight

The stabilizer was dissolved in the monomer, was then added to the water at 6O ⁰ C. The emulsion was formed in an emulsifying device in which the mixture was subjected to shear effects which were the same for all mixtures of the various tests. The initiator was then added with stirring and the monomers polymerized by using a water bath at 6O ⁰ C. After the polymerization, the degree of open cells in the structure was determined according to the VET test described above. The results are shown in Table I, in which the numerical values indicate the percentage of water removed in the VET test and the amount of alkyd stabilizer is expressed as a percentage by weight of the monomer. The number of the examples relates to the experiments carried out in the order according to their respective test series.

509825/03 6 2

Table I.

- 12 Alkyd % removed water Capric acid
Alkyd - 15 2.5 Linseed oil-
Alkyd example 14th 0.5 4.2 10 18th 0.38 3.6 13th 20th 0.25 36.8 0.12 35.7 17, 31.8 14.2 19 Tall oil
Alkyd 68.1 0.67 38.5 57.9 38.4

On the basis of the above criteria for interpreting the results (ie that VET values above 10% correspond to an open cell structure, while VET values below 3% indicate a closed cell structure) it can be seen that open cell structures can be obtained with all three alkyd resins provided that the alkyd resins are used in sufficiently small amounts. (All of these alkyd resins and stabilizers are very effective emulsifiers, and none of the concentrations mentioned have stability problems.) At concentrations above a critical concentration peculiar to the emulsifier (which was only achieved with two alkyd resins of the three alkyd resins tested), however, one results closed line structure.

5098 25/0962

Further analysis showed that the critical concentration is related to the reactivity. the the most unsaturated monobasic acid is found in linseed oil, while tall oil is only approximately half as unsaturated is like linseed oil. The linseed oil alkyd has reached its critical point Point in this special environment at a concentration between 0.38 and 0.5 wt. # Of the monomer, while the tall-

Oil alkyd its critical concentration in this environment only at concentrations of about 1.5 wt.% Of the monomer reached. The almost twice as unsaturated linseed oil alkyd (compared to tall oil alkyd) leads to closed cell structures at about half the concentration (compared to tall oil alkyd). Capric acid is saturated and, based on these considerations, a critical concentration should not be achieved with a capric acid alkyd. In fact, no closed cells were formed with this at any of the concentrations tested up to 2.5% by weight of the monomer. However, even with capric acid alkyd, when used in even larger amounts, a concentration is achieved at which excess emulsifier overcompensates for the degradation effect of its incompatibility with the polymer formed in the reaction, with the result that a closed cell structure is formed.

5098 2 5/0362

Examples 21 to 38 -

These examples form another set of experiments to demonstrate the way in which an emulsifier with negligible reaction, together with a set of polymerization reaction mixtures that create open cell structures in these mixtures, can become reactive in a different environment and form closed cell structures. Again, the selected emulsifiers were alkyd resins incompatible with the polymer so that the effects of changing the composition of the mixture on the changes in reactivity can be limited. All alkyd resins were reaction products of pentaerythritol, glycerol, polyethylene glycol, trimellitic anhydride and monobasic acid in molar ratios of 1/1/2/2/5 with the exception of Examples 51 to 34 in which the same compounds were used in molar ratios of 1.1 / 1.1 / 1.7 / 2/5 were used. The monobasic acids were different, but they were selected to give a series or series of alkyd resins with differing "unsaturation" and the procedure of Examples 10-21 above was followed using a constant weight of emulsifier (0.4 wt. repeatedly parts corresponding to 0.5% wt. of monomers). the monomers were also varied to achieve environments of different reactivities and the cell structure as checked before. Table II shows the results DIE

509825/0962

These tests, the numerical values given reflect the percentage of water loss according to the VET scale.

Table II

example Alkyd SZ Monomers MMA +
10 % ST BA +
5 %
ÄGDMA 21-23 acid 26th MMA 3.0 73.6 24 oleic acid 26th 11.7 75.4 25-28 stearin
acid * 18th 40.4 1.6 68.1 29-30 Tall oil . 0 38.5 13.4 80.9 31 - 34 Tall oil ** 25th 59.7 55.2. 74.2 35-38 Lauric acid 15.7 52.8 43.7 2.1 73.6 linseed oil 3.6

whereby

SZ

MMA

2-EHA

ST ÄGDMA

BA

Acid number

Methyl methacrylate 2-ethylhexyl acrylate Styrene

Ethylene glycol dimethacrylate butyl acrylate alkyd from Example 21, hydrogenated

Alkyd from Example 25 treated with diazomethane.

509825/0962

Example 39 to 42

These examples form a series of experiments »which shows how the reactivity of the emulsifier can be modified to achieve open or closed cell structures. In example 39, a "non-reactive" Capric acid alkyd used according to the preparation of Example. In Example 40, the free carbonyl groups were of the alkyd of Example 39 with glycidyl methacrylate (GMA) to convert it to a "reactive" emulsifier implemented. Example 41 made a "reactive" alkyd based on dehydrated castor oil fatty acids (DCO) was used, the preparation taking place as in the previous series of examples. The emulsifier from example 42 was prepared starting from that of Example 41, which was prepared by hydrogenating the dehydrated castor oil component had been made non-reactive. (The latter made a solution of bromine in carbon tetrachloride not discolored, which speaks for the loss of unsaturated components in the alkyd). The percent water loss was again determined after the VET test. The results are reproduced in Table III below.

509 825/0982

Table III

example Alkyd
(Acid) VET 39 · Capric acid 68.1 40 Capric acid + GMA 0.45 41 DCO 2.1 42 hydrogenated DCO 52.1

These results show how that in the polymer formation reaction The material produced becomes "closed-cell" when there is a significant reaction between the alkyd and the polymerizing mixture occurs and like an open cell structure by selection of the stabilizer components in can be obtained in such a way that negligible reaction occurs with a desired monomer.

Examples 45 to 46

These examples form a series of tests in which the emulsifiers were all of the same type, but with their components have been altered to produce varying degrees of incompatibility with that during the reaction polymers formed were obtained. In each case the emulsifier was essentially non-reactive with the polymerizing agent Mixture.

The emulsifiers were all from the two-

509825/0962

th type with a polymeric backbone with different attached components. In any case it existed the backbone of polymethyl methacrylate with a molecular weight (number average) of about 10,000. Monomethoxy polyethylene oxide chains (mol-

kular weight 750) at intervals "end-attached"; the respective Weight ratios are given in the table below. The emulsifiers of Examples 44 and 45 had pendant components of in addition to the pendant water-solvatable components Poly (12-hydroxy stearic acid) (molecular weight of about 2,000).

The emulsion was composed of 80 parts by weight of polymerizable liquid, 0.4 parts by weight of emulsifier, 320 parts by weight of demineralized water (pH 7.3) of 60 ⁰ C and i, 6 wt. Parts Initiator formed. A 75% active commercially available bis (4-tert-butyl-cyclohexyl) peroxydicarbonate sold under the name “Perkadox Y16 ^W ” was used as the initiator. In Examples 43 to 45, the polymerizable liquid was formed by methyl methacrylate and the emulsifier The backbone was of course soluble in the monomer and completely compatible with the polymer formed. In contrast, although poly (12-hydroxystearic acid) is soluble in the monomer, it is clearly incompatible with polymethyl methacrylate. In Example 46, the poly-

509825/0982

- "48 -

merizable liquid butyl acrylate and polybutyl acrylate incompatible with polymethyl methacrylate, which is the only component that can be solvated by butyl acrylate.

The emulsions were produced with different emulsifiers and "cured" at 60 ⁰ C. The water separated off after the VET test under reduced pressure is given in Table IV below as the percentage water loss on the VET scale.

Table IV

example Composition of
Emulsifier
(Weight) PMMA PHS Emulsions
stability water
tax (%) PEO 3 0 Well 0.2 43 1 1 1 poor. ** 40 44 1 1 2 η 67.4 45 1 3 0 Well 21.3 46 * 1

whereby PEO β polyethylene oxide with methoxy ends PMMA «polymethyl methacrylate PHS = poly (12-hydroxy stearic acid)

* polymer! izable liquid «butyl acrylate ** ann. = acceptable

509825/0962

Example 43 shows how the overcompensating compatibility of the excess polymethyl methacrylate of the emulsifier with the one formed in the reaction creates a closed cell structure. The intolerance induced by the poly (I2-hydroxy stearic acid) (Examples 44 and 45) leads to a consistent, very open structure. Example 46 shows the effect of incompatibility of polybutyl acrylate with the polymethyl methacrylate of the emulsifier, which in contrast to example gives rise to an open cell structure. It also illustrates how the emulsifier is repelled by the mixture without the use of incompatible monomer-solvatable components in the form of pendent chains can be obtained.

Examples 47 to 55

These examples form a series of experiments in which different alkyd resins were used as emulsifiers for emulsions in which the polymerization initiators were changed. The emulsions all consisted of methyl methacrylate (80 parts by weight), alkyd emulsifier (0.4 parts by weight), demineralized water of pH 7.3 (320 parts by weight) and polymerization initiator (1.6 parts by weight). parts). The emulsions were polymerized as before at 60 ^° C. and again with regard to the “openness” of the structure of the resulting polymer material according to the VET test described above

509825/0962

checked. Three different alkyd resins were used as Emulsifiers used, namely those of Examples 31, 25 and 35, respectively. These were again used for this series of experiments selected as illustrative material for different reactivities and they are in the below indicated in Table V by their specific acidity. The selected different initiators were "Perkadox Y16" (P-Y16) as a particularly active one monomer-soluble initiator which enables grafting reactions to be carried out by removing hydrogen is; Azo-valeronitrile (AVN) as a less active monomer-soluble Initiator and ammonium persulfate (AP) as one water soluble initiator. The results of these tests are given in Table V below, which shows the percentage water losses on the VET scale.

Table V

example initiator Alkyd acid Lauric
acid Tall oil linseed oil 47 - 49
50-52
53-55 P-Y16
. AVN
AP 52.8
39.6
0.8 38.5
31.6
1.1 3.6
44.1
0.9

509825/0962

As can be seen from Table V, lauric acid and tall oil both result in open cell structures with "Perkadox Y16 "and similar results are obtained with the azonitrile obtain. This was also to be expected after the above explanations, since there is no tendency for azonitrile to develop a to bring about significant reaction between the alkyd and the polymer-forming units, where any such Reaction with the more active peroxide initiator was negligible. The water-soluble persulfate delivers uniformly low VET values, suggesting the need to initiate polymerization within the bulk of the polymerizable en medium speaks.

Examples 56 to 61

These examples show different attempts to demonstrate the effect of branching in a molecule Alkyd emulsifier. The emulsion passed in all examples from methyl methacrylate (80 parts by weight), alkyd emulsifier (0.4 Parts by weight) and demineralized water of pH 7.3 ( Parts by weight). The water was added to a solution of the alkyd in methyl methacrylate and the various mixtures were subjected to equal shear effects to form the emulsions. The alkyd emulsifiers were through the reaction products of pentaerythritol (PE), glycerine (G), polyethylene glycol (PEG) with a molecular weight of 600, Trimellitic anhydride (TMA), adipic acid (AA) and one

50 9 8 25/0962

monobasic acid (MA) in the proportions given in Table VI below (including
of absence). Different monobasic acids were used; these are given in the table.

Table VI -

at
game Alkyd a
basic
acid Molar ratios pk G PEG TMA AA MA ^p OH ^p A Emulsion
stabili
activity 56.
57
'58
59
60
61 Tall oil
Lauric
acid
Tall oil
Caprine
acid
Caprine
acid
DCO 1
1.1
1.7
O
1.25
0 1
1.1 "
0
2.75
1.25
2.33 2
1.7
2
1.5
1.5
2 2
2
0
2
2
2 0
0
3
0
0
0 5
5
5
5
5
5 0.69
0.95
1.36
. 1.13
0.90
1.15 Well
Well
small amount
small amount
Well
small amount

where DCO = dehydrated castor oil.

"Good" means that the emulsion lasts for a week

was stable at ambient temperature;
"Low" means that the emulsion will be released after one hour

Showed signs of collapse (however, these alkyd resins have been shown to

B0982B / 0962

ren tests as "permanent emulsifiers" according to the explanation above).

The examples show how the use of a polyol with high functionality (e.g. pentaerythritol instead of glycerine) or by using acid with high basicity (e.g. trimellitic anhydride Instead of adipic acid) stronger branching can be obtained and the stability of the emulsion can be improved can.

In illustrating the effects of the different parameters on the cell structure of the during the polymerization formed material in the above description and in the illustrative examples, reference has been made to a range of alkyd resins, some of which are Representatives can deliver materials with an open cell structure and others a closed cell structure, what both depend on the alkyd resins themselves and on the environment in which they operate. Because of the nature and In the manner in which they are made, however, all alkyd resins contain a wide range of molecular types, and they result a new and very effective range of emulsifiers for use in the manufacture of water-filled resp. -expanded polymers, regardless of whether the resulting structure is open- or closed-cell.

5098 25/0962

As yet another aspect of the invention, a method for producing a water-filled or expanded polymer material is accordingly provided which comprises the formation of an inverse emulsion from a mixture comprising an aqueous liquid, a polymerizable liquid immiscible with water and an emulsifier , and subsequently the polymerization of the polymerizable liquid while maintaining the water in its disperse state, the emulsifier comprising an alkyd formed by a reaction product of a polyol with a functionality of more than 2, a water-soluble oxyethylated polyol, a polybasic acid or its anhydride and a monobasic acid having a carbon chain of at least 5 carbon atoms is formed. It should be noted that the emulsifier according to this aspect of the invention is not limited to one which gives negligible reaction with the polymerizing mixture or is incompatible with the polymer. The preferences set forth above other than those dictated by alkyd reactivity, that is, preferences in the choice of alkyd constituents and for the use of highly branched alkyd resins, are also preferences for these general purpose alkyd emulsifiers.

Corresponding to this further aspect of the invention

509825/0962

2A58887

the preferred method is one in which the emulsifier comprises an alkyd formed by the reaction product a polyol having a functionality greater than 2, polyethylene glycol, a polybasic acid, or theirs Anhydride and a long-chain fatty acid.

Similarly, in the above description and a further series of emulsifiers, i.e. those with a backbone, are described in the illustrative examples and pendant chain-like components used as a general-purpose emulsifier for the production of water-filled or expanded polymers are particularly useful, regardless of whether open cell structures are required to be or not.

Accordingly, we consider yet another aspect of the invention a method for producing a water-filled or -expanded polymer material provided that the formation an inverse emulsion of a mixture comprises, which comprises an aqueous liquid, a polymerizable, water-immiscible liquid and an emulsifier, after which the polymerizable liquid is polymerized while the water is in its disperse state is maintained, wherein the emulsifier comprises an amphipathic molecule which is a by the polymerizable liquid solvatable chain-like backbone and

509825/0962

has a plurality of chain-like components suspended from the spine which are carried by the aqueous liquid are solvatable and have molecular weights of at least 400, with the copolymers having an HLB value of less than 12 and preferably less than 9. As with the above alkyd resins, the emulsifier according to this is Aspect of the invention does not refer to one with negligible reaction with the polymerizing mixture or limited incompatibility with the polymer. However, the remainder (i.e. other than results of reactivity and compatibility) of the above statements with regard to such amphipathic molecules as well relevant to this general purpose aspect. These molecules are particularly useful as general purpose emulsifiers for the production of water-filled or -expanded polymers, given the ease with which they can get through Appropriate selection of the attached components can be brought into a form appropriate to a specific application can.

509825/0962

Claims (1)

Claims 1. Water-filled "or -expanded polymer material with an expansion of at least 65% and a VET value of at least 10 %. 2. Material according to claim 1, characterized by a VET value of at least 30 %. 3. Material according to claim 1 or 2, characterized by an average cell diameter of less than 10 pm. 4. Material according to one of the preceding claims, characterized by an expansion or stretching of at least 75 %. 5. Material according to one of the preceding claims, characterized in that it is by an addition polymer is formed by polymerizing a liquid monomer to a polymerizable therein ethylenically unsaturated group has been generated. 6. A method for producing a material according to claim 1, characterized in that an inverse emulsion is made produces a mixture that contains at least 65% by weight of an aqueous 509825/0962 rigen liquid, a polymerizable, water-immiscible liquid and an emulsifier and then the continuous phase of the emulsion is polymerized using a monomer-soluble initiator, using as an emulsifier an amphipathic material is used, which is a liquid which is polymerizable and immiscible with water a solvated component and another component which is solvated by the aqueous liquid is, and wherein the by the polymerizable, water-immiscible liquid solvated component a shows negligible reaction with the polymerizing reaction mixture and is incompatible with the polymer formed is. ?. Method according to claim 6, characterized in that a polymerizable liquid is selected which has a Ethylenically unsaturated monomer. 8. The method according to claim 6 or 7, characterized in that the proportions of the emulsifier are within a range of 0.02 to 5 wt.% Of the polymerizable liquid and in particular less than 1 wt. #, Preferably less than 0.5 wt. % the polymerizable liquid can be selected. 9. The method according to any one of claims 6 to 8, characterized in that 509 8 25/0962 indicates that the emulsifier is a simple block or alternating block copolymer with blocks of water-solvatable chain-like components is selected whose molecular weight is at least 400, the HLB value of the copolymer is less than 9. 10. The method according to any one of claims 6 to 8, characterized characterized in that an emulsifier is chosen, the amphipathic Comprises molecules having a chain-like backbone solvatable by the polymerizable liquid and a plurality of chain-like ones hanging from the spine Have components that can be solvated by the aqueous liquid and molecular weights of at least have, the emulsifier having an HLB value of less than 12, in particular less than 9. 11. The method according to claim 10, characterized in that that the emulsifier is suspended from the backbone by a plurality of solvatable by the polymerizable liquid chain-like components of a molecular weight of at least 400 in addition to the pendant components which can be solvated by the aqueous liquid. 12. The method according to any one of claims 6 to 8, characterized in that an arbitrary con- 509825/0962 Densation product is used, which consists of a polyfunctional Acid, a polyfunctional alcohol and a water-soluble oxyethylated polyol is formed. 13. The method according to claim 12, characterized in that the emulsifier is the reaction product of a polyol with an average functionality of at least 2, a water-soluble oxyethylated polyol, a polybasic one Acid or its anhydride and a monobasic acid having a carbon chain of at least 5 carbon atoms is. 14. The method according to claim 13, characterized in that the emulsifier has a gelling structure of the above defined type. 15. The method according to claim 13 or 14, characterized in that that the polyol constituent of the alkyd comprises a mixture of pentaerythritol and glycerine. 16. The method according to any one of claims 13 to 15, characterized characterized in that the oxyethylated polyol has a molecular weight in the range from 200 to 2,000, in particular in the range has from 400 to 1,000. 17. The method according to any one of claims 13 to 16, characterized 509825/0962 characterized in that the amount of that present in the alkyd
oxyethylated polyol in the range of 10 to 60 wt.% des
Alkyds lies. 18. The method according to any one of claims 13 to 17, characterized characterized in that the oxyethylated polyol is a polyethylene glycol. - 19. The method according to any one of claims 13 to 18, characterized in that the polybasic acid is trimellitic acid
or includes their anhydride. 20. The method according to any one of claims 13 to 19, characterized in that the monobasic acid is a carboxylic acid with a carbon chain of 5 to 22 carbon atoms
or an oil based thereon, and in particular through
a natural fatty acid with carbon chains of 12 to 18 carbon atoms or oils based thereon
will. 21. The method according to any one of claims 13 to 20, characterized in that the alkyd has an acid number in the range
has from 5 to 30 mg KOH / g. 22. The method according to any one of claims 13 to 21, characterized characterized in that the emulsion in addition to any 5.09825 / 0962 acid reactants used in preparing the alkyd contains a free acid in a proportion within the range of 0.5 to 5 % by weight of the polymerizable liquid. 23. The method according to claim 22, characterized in that the free acid by methacrylic acid, hydrochloric acid, Oleic acid or acetic acid is formed. 24. The method according to any one of claims 6 to 23, characterized in that the polymerization reaction at a Temperature above the glass transition temperature of the emulsifier component is carried out by the polymerizable Liquid becomes solvated. 25. A method for producing a water-filled or water-expanded polymer material, characterized in that an inverse emulsion is formed from a mixture containing an aqueous liquid, a polymerizable, with water immiscible liquid and an emulsifier, and which then polymerizes the polymerizable liquid while maintaining the water in its disperse state, the emulsifier comprising an alkyd which by the reaction product of a polyol with a functionality of more than 2, a water-soluble oxyäthylier- 5098 25/0362 ten polyol, a polybasic acid or its anhydride and a monobasic acid having a carbon chain of at least 5 carbon atoms is formed. 26. The method according to claim 25, characterized in that the emulsifier comprises an alkyd that by the reaction product from a polyol with a functionality greater than 2, polyethylene glycol, a polybasic one Acid or its anhydride and a long-chain fatty acid is formed. 27. A method for producing a water-filled or water-expanded polymer material, characterized in that an inverse emulsion is formed from a mixture containing an aqueous liquid, a polymerizable, with water immiscible liquid and an emulsifier and that then polymerizes the polymerizable liquid while the water is kept in its disperse state, the emulsifier is an amphipathic molecule comprises the one through the polymerizable liquid solvatable chain-like backbone includes and on Hanging from the backbone is a plurality of chain-like components that can be solvated by the aqueous liquid and have molecular weights of at least 400 with the emulsifier having an HLB of less than 12 and preferably owns less than 9. 50 9 8 25/0962 28. Water-filled or -expanded polymer, obtained according to one of claims 25 to 27. 509825/09 6 2