CH642985A5 - Foamable, RESIN COMPOSITION HAVING for producing foamed FORMKOERPER. - Google Patents

Description

642,985

PATENT CLAIMS

1. Foamable, resin-containing composition for producing foamed moldings by heating, characterized in that it (a) 100 parts by weight of resin based on polyvinyl chloride with an average degree of polymerization of not more than 2000 and a pore volume of not more than 0.20 ml / g contains and (b) at least a part by weight of at least one volatile foaming agent from the group consisting of aliphatic hydrocarbon compounds and aliphatic halogenated hydrocarbon compounds with a boiling point not above

Contains 90 ° C and wherein said polyvinyl chloride-based resin is impregnated with said foaming agent.

2. Composition according to claim 1, characterized in that it additionally contains (c) 0.5 to 30 parts by weight of a foam-regulating agent per 100 parts by weight of polyvinyl chloride-based resin, which is selected from the group consisting of acrylic resins and Styrene-based resins and (d) contains 0.01 to 20 parts by weight of a nucleating agent per 100 parts by weight of polyvinyl chloride-based resin.

3. Composition according to claim 1 or 2, characterized in that the polyvinyl chloride-based resin is a copolymer resin which is built up from 60 to 97% by weight of vinyl chloride and from 40 to 3% by weight of vinyl acetate.

4. Composition according to one of claims 1 to 3, characterized in that the resin based on polyvinyl chloride has an average degree of polymerization of at least 300.

5. Composition according to one of claims 2 to 4, characterized in that the foam-regulating agent has an intrinsic viscosity of at least 3.0 dl / g measured in a chloroform solution with a concentration of 0.1 g / 100 ml at 25 ° C.

6. Composition according to one of claims 2 to 5, characterized in that the nucleating agent is an inorganic powdery material which has an average particle size with a diameter of not more than 30 jun.

7. Composition according to one of claims 2 to 6, characterized in that the nucleating agent is a combination of an acid which is solid at room temperature and a carbonate or hydrogen carbonate of sodium, potassium or ammonium.

8. Composition according to claim 7, characterized in that the acid which is solid at room temperature is boric acid or an organic acid which is selected from the group consisting of citric acid, tartaric acid and oxalic acid.

9. Composition according to one of claims 2 to 8, characterized in that the acrylic resin is a poly-methyl methacrylate.

10. Composition according to one of claims 2 to 8, characterized in that the acrylic resin is a copolymer resin which is composed of methyl methacrylate and at least one acrylic ester selected from the group consisting of alkyl acrylates and alkyl methacrylates which differ from methyl methacrylates.

11. The composition according to claim 10, characterized in that the content of methyl methacrylate in the copolymer resin is in the range from 60 to 95% by weight.

12. Composition according to one of the claims 2 to 11, characterized in that the styrene-based resin is a copolymer resin which is composed of 90 to 40% by weight of styrene and from 10 to 60% by weight of a comonomer copolymerizable with styrene builds up.

13. The composition according to claim 12, characterized in that the comonomer which is copolymerizable with styrene is acrylonitrile.

14. Composition according to one of claims 2 5 to 13, characterized in that it additionally contains a decomposed

Lich foaming agent contains and in an amount not more than 5 wt .-%.

10th

The present invention relates to a foamable, resin-containing composition for producing foamed moldings.

According to the prior art, foams made from resins based on polyvinyl chloride (hereinafter, these are abbreviated as PVC resins) are produced by various processes. For example, (1) the resin is impregnated or mixed with a decomposable foaming agent, which is a decomposable compound that decomposes at an elevated temperature with evolution of a gas, and the resin mixture is processed by heating according to the techniques of extrusion, injection molding or other conventional molding agents, the resin being converted into foam by the gas formed by the decomposition of the foaming agent, (2) a so-called plastisol of paste-like consistency is first prepared by mixing the resin with a plasticizer and the like Plastisol is made into foams by introducing air, using suitable mechanical devices or, alternatively, the plastisol is further mixed with a decomposable foaming agent and the mixture is subjected to heating, whereby the foaming agent is decomposed to form a gas, which at the same time elution of the plastisol leads; (3) a resin mixture containing a decomposable foaming agent is first processed into molded articles, e.g. to plates, sheets, rods, tubes and the like, by rolling or using other suitable mechanical devices and working at temperatures which are lower than the decomposition temperature of the foaming agent and then heating the molded body in order to achieve the foaming by decomposing the foaming agent or that one

(4) Fills a metal mold with a resin mixture containing a decomposable foaming agent and optionally admixing it with a volatile foaming agent, an organic solvent with which the resin is swellable and a plasticizer, and heating the resin mixture under pressure in the metal mold so that it 50 is melted and gelled and then cooled to room temperature while the mixture is still in the metal mold under pressure, whereby a molded body is obtained, which is then heated again to a temperature above the softening point of the resin, causing the resin mixture to foam Foaming achieved with gas production through the decomposition or evaporation of the foaming agent.

As can be seen from the above description, the gas 6o which causes the resin mixture to foam and which is enclosed in the PVC resin foam is mostly either air introduced by mechanical devices or a gas which is a decomposition product of the decomposable foaming agents . The mechanical introduction and containment of air is, however, unsatisfactory because foams with a uniform and fine cell structure and high degrees of foaming are difficult to achieve, even using very complicated and sophisticated mixing devices, while the

55

3 642985

Use of a decomposable foaming agent is undesirable, so that resin foams with a maximum density of are when foams made of PVC resins with a high softness, for example, 0.10 g / cm 3 or less.

Degree of desirability is desirable because most of the practical uses have been made extensively by using decomposable foaming agents azo compounds to obtain a resin composition which are which lead to colored decomposition products and 5 to extremely high foaming ratio resin foams, corresponding to yellowish or brownish ones Colorings nis can be foamed and still a very fine foam material, which is produced and has a uniform cell structure and is achieved. In addition, the cellular structure of resin foams, an improvement in the composition described above, which is made with a decomposable foaming agent and impregnated with a volatile foaming agent, is not always satisfactory with respect to the PVC resin by changing from 0.5 to 30 wt . Parts of fineness and uniformity and especially when a foam conditioning agent per 100 parts by weight of foams with a high degree of foaming are desired. the PVC resin composition that comes with the foaming

In addition to the disadvantages mentioned above, the medium impregnation is inflicted. The foam conditioning methods 1 to 3 described above, not suitable for medium or foam conditioning resin, which will beat 15 here for the production of solid or semi-solid foams, is preferably either an acrylic resin or a high degree of foaming, i.e. the procedures use a styrene-based resin, which in detail is basic to the production of soft or flexi viscosity, in particular of at least 3.0 dl / g. The resin foams and the procedure (4) are disadvantageous. Effect of the above-mentioned foam conditioning resin from the standpoint of the yield and the production cost, is usually better expressed, especially when the procedure has to be carried out differently, 20 amounts of 0.01-20 wt. Parts of nucleating agent in which the time required for the production of a foam batch, not resin composition, are entered and it is maneuverably long because of the complexity, which is preferably a finely divided inorganic powder process. other materials or from a combination of solids. Another source of the gas in the resin foams is actants, which carbon dioxide gas due to the reaction in a volatile foaming agent which can release a compound 25 of the resin composition.

which has a relatively low boiling point and is the main component of the composition according to the invention.

which can easily be converted into a gas if the composition is a PVC resin, which is a homopolymer

Resin mixture containing this material is heated, or can be a copolymer, which is mainly based on Vi

that if the heating temperature is above the ethanol chloride. For example, if the PVC resin is a copolymer of the resin, resin foams are obtained, it is advantageous that the content of the mono-

the. This class of foaming agents is desirable because mers or the monomers that copolymerize with vinyl chloride

no colored decomposition products occur which are to be fermented, do not exceed 40% by weight, or would result in other staining of the resin foams, since the gas words that at least 60% by weight of the resin constituents do not form through decomposition, but only by vaporized vinyl chloride, from the standpoint that the so obtained

tion of the foaming agent is achieved. 35th resin foams excellent flame-retardant properties

The use of volatile foaming agents is possible, as well as high mechanical strength and other

have desirable properties in the manufacture of various types of plastic which

useful foam, e.g. are inherent in foams made of polystyrene resins.

zen, but there has been no effective process for the ethylenically unsaturated monomers associated with

The production of PVC resin foams has been described, although vinyl chloride can be copolymerized, the reasons for the difficulties are not yet fully known in the art. Examples of this are vinyl esters, as are clarified. e.g. Vinyl acetate and vinyl porpionate, vinylidene halides,

Accordingly, it is a goal of the present inventions such as Vinylidene chloride and vinylidene fluoride, vinyl halide

to provide a novel composition other than vinyl chloride, e.g. Vinyl flow

which are used for the production of foams from PVC orid, acrylic acids and esters thereof, e.g. Ethyl acrylate

Resins is suitable, and which is a volatile foaming and methacrylic acid and its esters, e.g. Methacrylate,

contains medium, with high foaming resin foams acrylonitrile, methacrylonitrile, maleic acid and ester and

degree of efficiency and fine and uniform cell structure on hydril thereof, fumaric acid and esters thereof, and olefins,

can be properly preserved without any Ethylene and propylene.

detectable staining occurs. Among the comonomers mentioned above, vinyl acetate is particularly advantageous in the compositions comprising the resin according to the invention, because a copolymer of vinyl chlorides can be foamed to form foams and contain a rid and vinyl acetate which is not only impregnable with a foaming agent PVC resin with an average degree of polymerization, but also has a significantly reduced of no more than 2000 and an average pore volume of 55 melt viscosity, so that suppleness in the lumen of not more than 0.20 ml / g of the resin, as well as min foaming, is achieved, whereby one forms a weight by weight Part of at least one volatile resin foam arrives, which has a further improved and foaming agent, which have a hydrocarbon or a uniform cell structure. That such a pre-halogenated hydrocarbon is expected to have a boiling point partial effect due to the use of the not more than 90 ° C and the above-mentioned PVC-6Q copolymer, the content of vinyl acetate in the copoly resin should be impregnated with this foaming agent is. mer resin more advantageously comprise at least 3 wt .-% and up to 40% by weight in the above-described resin-containing composition to form foams with a high foaming with respect to the flame retardant properties and the degree be foamed, whereby satisfactorily fine and mechanical properties of the resin foam obtained in this way, uniform cell structure was achieved in most cases.

becomes. The parameters that are important for the PVC resins

However, the cell structure is not always so fine and one that is present in the resin compositions according to the invention

When the foaming ratio is extremely high, the average polymerization is uniform

642 985 4

degrees and the pore volume. The average polymeric 1,2-dichloroethane, trichlorofluoromethane, dichlorodifluorosation degree, which can easily be determined by measuring the solution viscosity, chlorotrifluoromethane, bromotrifluoromethane, tetrafluority of the resin, is not more than 2000, methane, dichlorofluoromethane, chlorodifluoromethane, trllorofluoromethane -As a PVC resin with an average crosslinking methane, trichlorotrifluoroethane, dichlorotetrafluoroethane, di-degree of more than 2000 has an extremely high melt viscosity s bromotetrafluoroethane, chloropentafluoroethane, hexafluoroethane and poor gelation, so that resin foams, 1 -chloro- 1,1-difluoroethane and the like. Of course, these volatile foaming agents can only be obtained with difficulty with a high degree of foaming, even with a large amount of foaming agents, not only individually, but also in combinations of two with which the resin is impregnated. On the other hand, or more substances are applied.

becomes the lower limit of the average polymerization. The amount with which the PVC resin having the above-mentioned degrees by considering the mechanical properties of volatile foaming agents is impregnated with the resin foams, which using this resin depends on the desired degree of Foaming to be determined. For example, you can start from egg resin foams. It can be too extensive if you find a PVC resin with an average polymeriza- that the amount to be impregnated with less than 300 only fragile and mechanical 15 must be increased if a foamed body with niche produce inferior resin foams. high foaming ratio is desired, and if

Another important parameter for the PVC resins in a foamed body with a low foaming composition according to the invention is the pore ratio is desired, an amount such as e.g. 3 volume, which should not exceed 0.20 ml / g and, more preferably,% by weight or less foaming agent impregnation, 0.10 ml / g resin, the value 20 sometimes being sufficient. The amount of foaming with this pore volume is quite small compared to usual but is in most cases between 1 and 30 wt .-% PVC resins, which is about 0.25 ml / g or more Po or more and in Sufficient in most cases if they have a volume, if the resin is a homopolymer foamed molded article with sufficient foaming of vinyl chloride. The pore volume is a value that should be obtained.

usually with a mercury pressure porosity meter 25 The impregnation of the PVC resin with a volatile is determined, the mercury pressure of 1 on foaming agent, as mentioned above, is in principle

100 kg / cm2 is increased, so that the mercury in the pores is carried out in such a way that these components are penetrated by resin particles which bring a pore diameter into contact. In particular, the PVC resin may be about 30 µm or less. powdery form simply with the foaming agent

The above-mentioned restriction regarding pore 30 mixing, so that the foaming agent in the resin volume is very essential because of a PVC resin that absorbs a particle. If the foaming agent has a larger pore volume, is gaseous with respect to the retention room temperature under atmospheric pressure, is less effective than the foaming agent and can be used as a suitable procedure for the impregnation of the foaming agent's lust not only during storage of PVC resin, that the PVC of the resin composition, which is impregnated with the foaming agent, resin, water and a dispersing agent, into a lower part occurs, but also during the pressurizable container, for example an autoclave,

Introduces molding process of the resin composition into one which is equipped with an agitator to provide resin foam molded articles, so that foamed molded articles are difficult to obtain a suspension of the resin powder in the aqueous medium with a high foaming ratio, and then the foaming agent will be in the can. 40 suspension introduced under pressure, and then stirred

The PVC resins which meet the above-mentioned requirements to mix the mixture by raising the temperature to 30 to 100 ° C are obtained by suspension poly 90 ° C for 3 to 20 hours. After the absorption of vinyl chloride monomers or a monomer equilibrium has set in within the container and the mixture, which mainly consists of vinyl chloride mono- the mixture has cooled to room temperature, the meren is built up in an aqueous medium, 45 resin, which has absorbed the foaming agent, from which a suspending agent is removed in the presence of a polymer container and, using suitable devices, initiators in the form of free radicals, which are dehydrated in the, for example by centrifugal separation, and monomeric phase are soluble. one dries under a stream of air at a relatively low

The volatile foaming agent with which the above-mentioned temperature of, for example, 50 ° C or lower, where-described PVC resin is to be impregnated, is, as by obtaining the desired PVC resin, which is mentioned with a hydrocarbon or a halogenated one is impregnated with the foaming agent. Hydrocarbon compound having a boiling point of The resin composition thus prepared, which is impregnated with not more than 90 ° C, and preferably not more than the volatile foaming agent, can now be 70 ° C because if a foaming agent is molded into resin foam articles according to any be-with a boiling point of more than 90 ° C, known procedures are processed, such as by the resin foams after their foaming show a clear injection molding or explosion molding, as well as by pressure shrinkage when left to stand, so that the molding obtained in this way in a metal mold in which gelation of the hard foam has a cell structure, zes and expansion of the gelled resin due to the unsatisfactory softening of the foaming agent, the gas of the foaming agent formed at the same time being uniform. occurs. Optionally, the resin composition can be pre-

The hydrocarbon or halogenated hydrocarbon processing with certain types of additives, serie compounds, which are mixed in the inventions according to the invention, which are usually used in the molding of compositions for use as foaming agents, such as PVC resins, e.g. Plasticizers are suitable; are, for example, propane, butane, isobutane, pen- 65 flame retardants, antioxidants, antistatic wir-tan, neopentane, n-hexane, isohexane, n-heptane, methylchlo- cing agents and the like, with one being a relatively low-methylene chloride , Chloroform, carbon tetrachloride, temperature works to prevent premature evaporation of ethylidene chloride, ethylidene fluoride, trichlorethylene, the foaming agent.

5,642,985

As mentioned earlier, one of the more difficult processes of acrylic resin than the ones mentioned above does not result in any further problems in obtaining a foamed body from PVC replacement and instead resinizes undesirable effects, which ensure the delicacy and uniformity of the properties that the PVC-Har-the cell structure of the resin foams, especially if the zen are peculiar, such as flame retardancy. Foaming ratio of the foam is extremely high or 5 styrene-based resins belong to another class of when the foams mentioned have a bulk density of, for example, foam conditioning resins. The styrene-based resins are 0.10 g / cm3 or less. This depends on homopolymers of styrene, but it is still understandable from the manufacturing conditions that it is preferable that the styrene-based resins are copolymers, foams that have a bulk density of about 0.30 g / cm3 which are mainly based on styrene and one can have. Corresponding investigations have been carried out containing a smaller proportion of acrylonitrile as a comonomer, in order to condition the cell structure. It is of course possible, if appropriate, for the Co to achieve this, and it has been found that the addition of a polymeric one or more of other comonomers de-foam conditioning agent to the resin composition, which is copolymerizable with styrene and acrylonitrile favorable, and it was concluded that the additive. In any case, the styrene-based resin should usually be of certain types of thermoplastic resins, in particular an intrinsic viscosity of at least 3.0 dl / g, measured in particular if it is suitable for this purpose. ner chloroform solution with a concentration of

The foam conditionings which can be used according to the invention have 0.1 g / 100 ml at 25 ° C. It is recommended that resin resins include acrylic resins and styrene-based resins, the styrene-based resin has an intrinsic viscosity, and these resins are particularly effective when they are as high as possible when the resin is based on vinyl chloride.

Basic viscosity of at least 3.0 dl / g, measured in a 20 basis, a high average degree of polymerization

Chloroform solution with a concentration of 0.1 g / 100 ml, which approaches the upper limit of 2000. Which have at a temperature of 25 ° C. These foam comonomers mentioned above, which are coated with styrene and acrylic

Conditioning resins are expediently copolymerizable with the PVC nitrii, for example esters of

Resin mixed with the volatile foaming agent in acrylic acid, e.g. Methyl acrylate, ethyl acrylate, n-butyl

is impregnated in an amount of 0.5 to 30 parts by weight / 100 25 acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and the like,

Parts by weight PVC resin, which with the foaming ester of methacrylic acid such as Methyl methacrylate, ethyl agent is impregnated, mixed before the resin composition methacrylate, n-butyl methacrylate, 2-ethyl hexyl methacrylate is formed into molded articles from resin foams. The and the like, maleic acid and fumaric acid and esters thereof

Acrylic resins, which are suitable as foam conditioning agents and maleic anhydride.

are either polymethyl methacrylate or copoly 30 The above-mentioned styrene-based resins are obtained after merharze, mainly built up from methyl methacrylate usual procedures for the polymerization,

and one or more acrylic esters, e.g. Methyl acrylate, but it is recommended that the resin be

Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexylation is produced in an aqueous medium.

acrylate and the like. The acrylic resins can also be como. The amount of styrene-based resin contained as foam nomers other than the above-mentioned conditioning agents can be the same as e.g. Styrene, acrylonitrile, vinil ester and esters of meth- as in the case of acrylic resins, i.e. in the range of about acrylic acid other than methyl methacrylate such as e.g. 0.5 to about 30 parts by weight or preferably from 3 to 20 parts by weight

Ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl meth parts by weight / 100 parts by weight of the PVC resin, which with acrylate and the like, which ensures that the content is impregnated with the volatile foaming agent.

is limited to these components. In any case, the mechanism by which the significant

the content of methyl methacrylate in the acrylic resins should preferably be in the range from 60 to 95% by weight with regard to the cell structure of the foamed. Resins by adding the foam conditioning resins

It is desirable that the acrylic resin be given as a foam condition, probably due to the gelatin

resin usually has an intrinsic viscosity that minimizes the PVC resin due to the foam conditioning

at least 3.0 dl / g or preferably from at least 5.0 dl / g resin is accelerated and the melt viscosity of the PVC

exhibit, measured in a chloroform solution with a Kon resin in the molding step suitably controlled concentration of 0.1 g / 100 ml at 25 ° C, as mentioned above. is or is increased so that the expandability of the

It is recommended that an acrylic resin with a larger foam is raised and the cell walls of the foam

Basic viscosity or in other words, to be strengthened with one, so that they have a higher resistance to use higher average degree of polymerization against flow into one another (coalescence) or

that if the average degree of polymerization of the foams have, as well as that the shrinkage

PVC resin is very large and approaches the upper limit of 2000 when a foam is formed with an increased one. Furthermore, an acrylic resin is preferably to be used. Temperature is prevented with improved recovery.

the one obtained by the emulsion polymerization of the acrylic gas, which was obtained by the evaporation of the nomer, because additional improvements were made to the foaming agent.

are obtained when such a resin is used, and it has further been found that the foam conditioning effect described above with regard to the smoothness of the introduction into the mold, which is achieved by the machine with a reduced risk of blocking a foam conditioning resin , white inlet for the resin composition, which is reinforced in the fore when certain types of nucleation direction are filled, and in addition, this contributes to the acceleration of the uniform gel formation of the composition together with the foam conditioning resin are. A class of nucleating agents that are invented and suitable for increasing the foamability of the gelled and according to the invention are inorganic fine powder-molded resin compositions. shaped materials such as Calcium carbonate, talc, Ba-The amount of acrylic resin to be added as foam conditioning sulfate, sublimed silicon oxide, titanium dioxide, alumina, solvent is in the range of 0.5 65 aluminum oxide, bentonite, diatomaceous earth and the like with up to 30 parts by weight and preferably from 3-20 parts by weight, an average particle diameter of 30 µm / 100 parts by weight of the PVC resin, which is impregnated with the or less and preferably of 10] xm or less because foaming agent is because of larger amounts coarser particles of these inorganic powders that flow

642 985 6

of the molten resin in the shaping step after-influence resin foams with a high foaming ratio in part, so that the surface properties of and with a fine and uniform cell structure results in independent foamed bodies which are obtained with the addition of such a large amount of the strength of the desired foamed progroder powder , adversely affected products, which can range from soft and flexible to hard and resilient, with regard to the gloss and sometimes streak-like materials, if one has the usual continuation and poor uniformity of the cell structure. Another manufacturing class of nucleating agents is extrusion molding, injection molding, die casting and combination of approximately equivalent amounts of an acid, the like, without incurring any special cost factors such as e.g. Boric acid, and organic acids, e.g. Citrators must be taken into account.

Nenoic acid, tartaric acid and / or oxalic acid and a carbo- 10 The invention is now based on the following examples, which relate to sodium carbonate or hydrogen carbonate or preferred embodiments of the invention.

monium, such as Sodium carbonate, sodium bicarbonate explained. In the examples, all parts are bonat, potassium carbonate, ammonium hydrogen carbonate and parts by weight. The procedure for determining the amount of

similar. volatile foaming agent with which the PVÇ resin

The amount of nucleating agent impregnated in Kombina and the determination of the pore volume of the ion used with the foam conditioning resin are as follows:

is generally in the range from 0.01 to 20. The amount of impregnation with volatile foam

Parts by weight per 100 parts by weight of PVC resin, which follows with the agent as follows: The PVC resin, which with the

Foaming agent is impregnated. When the amount of volatile foaming agent is impregnated, it is mixed in one

If the nucleating agent comprises more than 20 parts by weight, 20 air furnaces are heated at a temperature of 130 ° C. for two hours, the expansion ratio of the foamed resin is reduced, and the extent of the impregnation is changed and the foamed molded articles obtained in this way are calculated by the equation (W, - W2) / W2 x 100

ben applied deteriorated properties, including less (%), with Wt and W2 being the smoother surface in this equation. Weight before and after heating.

The pore volume of the PVC resin was composed as follows with known decomposable foaming agents: The measurement was carried out using a mercury pressure agent, provided that its amount was used, for example, model 70H porosimeters from Carl Erba Co. , increasing 5 parts by weight or less per 100 parts by weight of the PVC pressure of mercury from 1 to 100 kg / cm 2, resin impregnated with the volatile foaming agent and the porosity expressed in milliliters per gram is limited. The decomposable foams of the resin.

Detergents which are suitable for use are, for example, azo compounds, e.g. Azodicarbonamide, Example 1

Azobisiobutyronitrile, Diazoaminobenzol, Diethylazodicarb- (Experiment No. 1 to 13)

oxylate, diisopropylazodicarboxylate and the like, nitroso- In an autoclave with a capacity of 5 liters, which

connections such as N, N'-Dinitrosopentamethylenetetra- 35 rather equipped with a stirrer, 1000 g were

min, N, Nr-dimethyldinitrosoterephthalamide and similar vinyl chloride homopolymers or a copolymer resin

and sulfonyl hydrazide compounds such as e.g. Benzenesulfonyl, which consists of vinyl chloride and vinyl acetate in Table 1

hydrazide, toluenesulfonylhydrazide, 4,4'-oxy-bis (benzenesulfo-given, and where P and Vp for a nylhydrazide), 3,3'-di (sulfonhydrazidphenyl) sulfone, toluenedi-average degree of polymerization and the pore volume sulfonylhydrazone, Thio-bis (benzenesulfonylhydrazide), toluene- 40 men of the resin stand, as well as 2000 g of purified water and sulfonyl azide, toluenesulfonyl-semicarbazide, 4,4'-oxy-bis (ben- 150 g trichloro-fullormethane and 200 g of benzenesulfonylhydrazide) and similar as well as sodium hydrobutane introduced under pressure and then heated gencarbonate. with stirring to 70 ° C and the stirring led to the same

The application of such decomposable foaming agent temperature for 8 hours to the resin agent is desirable to maintain the delicacy and uniformity of cell 45 trichlorofluoromethane and butane as a volatile foaming agent.

to further improve the structure of the resin foams and to impregnate them. After cooling to room temperature

To reduce shrinkage of the foamed molding, tur and unloading of the excess foaming agent so that the molds of the foamed molding better in the autoclave, the resin impregnated in this way is retained, although too much of the decomposable autoclave is removed and placed under an air stream 40

Foaming agent undesirable is dewatered due to the color 50 to 50 ° C for 8 hours.

of the foamed molding by the colored decomposition- The amount of the impregnation with foaming agent in the tongue products thereof and the rougher surface properties- resin was immediately after the production and after the layer-

foamed molded articles without any determination at 20 ° C for a week and

additional benefits can be achieved. It also contains the results that are already given in the table,

failing to add a decomposition accelerator, such as 55 The resins contained above, which are known from the prior art with foaming agents, e.g. are impregnated in an amount of 100 parts by weight

certain types of zinc bonds, copper compounds with 2 parts of the tin-containing stabilizing agent and the like, in order to mix the decomposition of the decomposable foam and a part of caldum stearate and to mix the resin

agent and the gas formation at a low temperature was formed into a foamed molded body in the form of

processed below the molding temperature of the resin composition of the cylindrical rod by extrusion

accelerate the tongue. using an extruder that

The foamable resin composition described above was operated as indicated below

Settling with the addition of a foam conditioning agent.

The bulk density of the foamed molded body in each body made of PVC resin foams, because the composition was obtained from the experiment, is given in the table.

Operating conditions of the extruder: screw diameter 20 mm

Screw length 400 mm

Compression ratio of the screw 3.0

Extruder nozzle 5 mm 0 at the

Opening and 70 mm nozzle length sieves one with 80 mesh

Openings and one with 100 mesh openings

Table 1

Experiment No. 1 2

PVC

Content of

5

10th

resin

Vinyl acetate,% by weight

P

350

400

Vp, ml / g

0.009

0.010

Impregnation with

When manufacturing

8.0

10.1

Foaming agent,

% By weight

After 1 week at 20 ° C bulk density of the

7.5

9.4

Foam body, g / ml

0.073

0.065

Temperature of the

Cylinder Q = 60 to 120 ° C

C2 = 100 to 160 ° C C3 = 120 to 180 ° C temperature of the nozzle about 130 ° C

Speed of rotation 50 revolutions per minute

The foam body obtained in Experiment 9 was very brittle. Although the foam body obtained in Experiment 11 had a high foaming ratio, it was inferior in flame retardancy.

3 4 12 0 520 700

5

20 800

6

30th

7

40

40

9

10th

10 5

11 45

12 3

0.009 0.035 0.015 0.020 0.080 0.12 11.0 9.4 9.5 7.5 7.0 7.5

1,000 1,300 1,800 270 2,500 810 700 0.010 0.20 0.020 0.25 9.0 7.4

10.4 8.5 0.060 0.19

0.11

7.0 0.21

6.5 0.23

6.0.

0.25

8.0 0.14

5.6 1.35

9.5 8.5 0.10

2.5 0.8 1.2

13 0

1,000

0.35

1.9

0.3

1.35

£ K>

£ m

Example 2

(Experiments 14 to 26)

In the same autoclave as used in Example 1, 1000 g of a copolymer resin of 88% by weight of vinyl chloride and 12% by weight of vinyl acetate was introduced, which had a pore volume Vp of 0.010 ml / g and an average degree of polymerization P of about 650, then 2000 g of purified water and 1.0 g of partially saponified polyvinyl alcohol and further one or 2 types of volatile foaming agent as shown in Table 2 below in the amounts which are also shown in the table were introduced into the autoclave and if necessary , pressure was applied, followed by stirring at 70 ° C for 8 hours to impregnate the resin with the foaming agent.

The notation for the volatilizable foaming agents as used in this example is as follows and continues to be used in other examples:

Table 2

Experiment No.

14

15

16

17th

18th

Foaming agent

PR

PE

HE

TCFM

MC

(G)

(300)

(300)

(300)

(300)

(200)

-L

i

PE

(200)

Impregnation with

Foaming agent,

% By weight

8.1

8.5

10.2

19.0

20.1

Bulk density

of the foamed

Shaped body g / ml

0.13

0.13

0.24

0.09

0.13

PR: propane PE, pentane HE: n-hexane

TCFM: trichlorofluoromethane MC: methyl chloride BU: butane

MEC: methylene chloride DCTFE: dichlorotetrafluoroethane DCDFM: dichlorodifluoromethane DCFM: dichlorofluoromethane TCE: 1,1,2-trichloroethane TCDFE: tetrachlorodifluoroethane ISO: isooctane

The amount of the impregnation with the foaming agents and the bulk density of the foamed moldings in the form of cylindrical rods which were produced in the same manner as in Example 1 are given in Table 2. The foamed moldings of Experiments No. 24 to 26 showed severe shrinkage after molding.

19th

20th

21st

22

23

24th

25 26

BU

BU

TCFM

DCTFE DCDFM

TCE

TCDFE ISO

(300)

(200)

(200)

(100)

(150)

(200)

(200) (200)

* + *

+

+

+

MEC

PE

TCFM

DCFM

(100)

(200)

(200)

(150)

10.5

14.7

18.3

20.4

18.1

11.0

10.2 7.9

0.10 0.07 0.08 0.09 0.09 0.75 0.80 0.87

Example 3

(Experiments No. 27 to 33)

In a stainless steel autoclave with a capacity of 100 liters, which was equipped with a stirrer, 30 kg of the same polymer resin of vinyl chloride and vinyl acetate as used in Example 2, 50 kg of purified water and 15 g of a partially saponified polyvinyl alcohol and a mixed foaming agent of butane and trichlorofluoromethane in a ratio of 2: 1 was introduced and pressure was applied in the autoclave to the extent indicated in Table 3 below, and the resin was impregnated with stirring for 8 hours in a Temperature as it is also given in the following table with the foaming agent. The drainage and drying of the resin impregnated with the foaming agent was carried out in the same manner as in Example 1. The amount

9 642985

the impregnation with the foaming agent is given in Table 3.

Resin mixtures were prepared with 100 parts each of the foaming agent-impregnated resins obtained above, two parts of a tin-containing stabilizing agent and one part of calcium stearate, and the resin mixture was molded into foamed molded articles in the form of sheets by using extrusion molding using the extruder operating under the white conditions below.

The foamed molded articles thus obtained were subjected to the determination of the bulk density, the thermal conductivity at 20 ° C according to the method specified in JIS under A1413, and also the compression strength 15 at 20 ° C was measured according to the procedure ASTM D 1621, which gave the results shown in Table 3.

Operating conditions of the extruder:

Screw diameter Screw length Compression ratio of the screw nozzle sieves

Temperature of the cylinder

Temperature of the nozzle rotation speed

65 mm 1300 mm

2.0

100 mm wide and 8 mm high, one with 80 mesh openings and one with 100 mesh openings

C, = 80 ° C

C2 = 120 ° C

C3 = 150 ° C

120 ° C

30 revolutions per minute

Table 3 Experiment No. Amount of mixed foaming agent, kg temperature, ° C impregnation with foaming agent; % By weight

Properties of the foamed molding

Bulk density,

g / ml

Thermal conductivity kcal / hour ° C Compression resistance kg / cm

27th

28

29

30th

31

32

33

3rd

6

8th

11

6

6

0.6

70

70

70

70

35

85

70

5.0

8.2

12.1

13.3

9.1

10.9

0.8

0.18

0.080

0.059

0.058

0.070

0.061

0.9!

0.043 0.037 0.035 0.031 0.035 0.034 0.10 39.0 11.2 6.0 6.3 9.3 7.8 450.0

Example 4 (Experiments Nos. 34 to 43)

The procedure for producing the copolymer resin of vinyl chloride and vinyl acetate impregnated with a mixed foaming agent of trichlorofluoromethane and butane was the same as in Example 1, except that the resin used had a vinyl acetate content, an average degree of polymerization P and had a pore volume Vp as shown in Table 4 below. The amount of the impregnation with foaming agent was determined immediately after production and after one week of storage at 20 ° C., as indicated in the table.

55 The expandable resin compositions were each made by adding 100 parts of the above-prepared copolymer resins impregnated with foaming agent with 2 parts of a tin-containing stabilizing agent and one part of calcium stearate together with or without addition of one part of talcum as a nucleating agent and one part of decomposable Foaming agent on an azodicarbona-mid compound, available under the name Celmic 133 from Sankyo Kasei Co., Japan, and either one of the acrylic resins El and E-2, which are explained in more detail below, in the amounts given in Table 4 are.

The acrylic resins which were used as foam conditioning agents in the experiments and as E-1 or

642985

10th

E-2 listed in the table were the following products:

E-l: A copolymer resin consisting of 90% by weight of methyl methacrylate and 10% by weight of ethyl acrylate with an intrinsic viscosity of 10 dl / g at 25 ° C in a concentration of 0.1 g / 100 ml in chloroform solution.

E-2: A commercially available acrylic resin available under the trade name Paraloid K-120 from Rohm & Haas Co.

The foamable resin compositions were made into foamed molded articles by using extrusion molding using the same extruder and under the same operating conditions of the device as in Example 1, and the foamed molded articles were evaluated for the bulk density under the cell structure, and the results were obtained. as shown in Table 4. The evaluation of the cell structure, which is given in the table, was carried out according to the following standards:

5 Cell structure A: diameter of the cells, not exceeding 500 micrometers

Cell structure B: diameter of the cells in the range from 500 micrometers to 2000 micrometers

The foamed molded body, which in experiment no.

1040 was clearly brittle. In experiment No. 43, the composition foamed early while the composition was still in the nozzle, which caused flow marks to appear on the surface of the foamed molded article.

Table 4-1

Experiment No. 34 35 36 37 38

PVC content of

Vinyl acetate,

Content and% by weight

12

12

5

20th

30th

resin

P

520

520

350

700

1000

Vp, ml / g

0.010

0.010

0.009

0.012

0.020

Impregnated

At Her

tion with position

11.0

11.0

8.0

10.3

7.5

mixed

After a

Foaming

Week at

medium weight%

20 ° C

10.3

10.3

7.4

9.7

7.0

Nucleating agents

Yes

Yes

Yes

Yes

Yes decomposable foaming agent

No

Yes

Yes

Yes

Yes

Acrylic resin (parts)

E-l

E-l

E-2

E-2

E-2

foam

(10.0)

(10.0)

(6.0)

(6.0)

(6.0)

Cutting density

body g / ml

0.050

0.045

0.050

0.051

0.10

Cell structure

A

A

A

A

A

Table 4-2

39

40

41

42

43

40

10th

30th

2nd

45

1300

270

1600

800

810

0.023

0.010

0.050

0.060

0.020

7.0

9.0

6.0

6.9

9.5

6.6

8.0

4.0

5.4

8.5

Yes

No

No

No

No

Yes

No

No

No

No

E-2 (6.0)

no no no no

0.20

0.14

0.30

0.23

0.11

A

B

B

B

B

Example 5:

(Experiments No. 46 to 56)

In the same autoclave as used in Example 4, 1000 g of the same copolymer resin consisting of vinyl chloride and vinyl acetate as used in Example 2, 2000 g of purified water and 1.0 g of partially saponified polyvinyl alcohol and one or a combination of 2 of the volatile were Foaming agents, as shown in Table 5 below, were introduced in the amounts as also given in the table under pressure and then stirred at 70 ° C for 8 hours to add the resin with the foaming agent or foaming agents impregnate. The amounts of impregnation with the foaming agent are given in Table 5.

Foamable resin compositions were prepared by mixing 100 parts of the copolymer resin impregnated with the volatile foaming agent, one part (Experiments Nos. 46 to 48) or three parts (Experiments Nos. 49 to 56) of a nucleating agent as shown in Table 5 , with or without the addition of six parts of an acrylic resin (Metablen P551, a trademark of Mitsubishi Rayon Co., Japan) as foam conditioning agent.

The nucleating agents used in the experiments were as follows:

50 orben: An organic complex of colloidal hydrated aluminum silicate with an average particle diameter of about 0.5 µm, a product of Shi-raishi Calcium Co., Japan.

Hakuenka O: A calcium carbonate filler with an average particle diameter of 0.02 to 0.03 µm, a product of Shiraishi Calcium Co., Japan.

Titanium Dioxide A-100: A filler, quality titanium dioxide with an average particle diameter of about 0.15 to 0.25 µm, a product of Ishihara Sangyo Co., 60Japan.

Aerosil 200: A sublimed siliconoxy filler material with a specific surface area of about 200 m2 / g and an average particle diameter of about 6_0.012 (im, a product of Nippon Aerosil Co., Japan.

Aerosil 380: A sublimed silica filler material with a specific surface area of about 380 m2 / g and an average particle diameter of about 0.002 (im, a product of Nippon Aerosil Co., Japan.

A1203C: An alumina filler with an average particle diameter of about 0.005 to 0.02 µm, a product of Nippon Aerosil Co., Japan.

Barium Sulfate # 100: A product of Sakai Chemical Co., Japan, with an average particle diameter of approximately 0.6 (im.

Satenton No. 5: An alumina product from Tsuchiya Kaolin Co., Japan.

3S Tale: A Talcum product from Nitto Funko Kogyo Co., Japan.

11 642 985

The expandable resin compositions thus prepared were made into foamed molded articles in the form of cylindrical bars by using extrusion molding using the same extruder and operating conditions as in Example 4, and the foamed molded articles were compared the bulk density was assessed and the data given in Table 5 were obtained.

Table 5-1

Experiment no.

46

47

48

49

50

Vaporizable

PR

PE

TCFM

BU

BU

Foaming agent

(300)

(300)

(300)

(300)

(200)

(G)

+

MEC

(100)

Impregnation with

Foaming agent

% By weight

6.5

7.0

15.4

7.3

11.0

Nucleating agents

Orben

Orben

Haku

titanium

Aeros

enkaO

Dioxide

200

A-100

removable

Foaming agent

No

No

No

No

No

Acrylic resin

Yes

Yes

Yes

Yes

Yes

Bulk density of

foamed shape

body, g / ml

0.089

0.093

0.077

0.080

0.039

Table 5-2

51

52

53

54

55

56

TCFM

TCFM

TCFM

TCFM

TCDFE

iso

(200)

(30)

(100)

(200)

(200)

(200)

+

+

+

+

PE

BU

BU

BU

(100)

(30)

(100)

(400)

12.4

3.4

8.2

15.0

9.8

7.4

ai2o3c

barium

Tale

Clay

Aerosil

Haku

Sulphate # 100

380

enkaO

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

Yes

No

No

0.059

0.15

0.073

0.030

0.70

0.81

Example 6 (Experiments Nos. 58 to 71)

In an autoclave with a capacity of 100 liters, which was made of stainless steel and equipped with a stirrer, 30 kg of copolymer resin consisting of 88% by weight of vinyl chloride and 12% of vinyl acetate, which had an average degree of polymerization P of about 850 and a Pore volume Vp of 0.015 ml / g had, 50 kg of purified water, 15 g of partially saponified polyvinyl alcohol and 6 kg of trichlorofluoromethane and another 3 kg of butane filled under pressure and then stirred at 70 ° C for 8 hours to the resin with trichlorofluoromethane and butane to be impregnated as a volatile foaming agent. After completion of the impregnation and cooling to room temperature and draining off the excess foaming agents, the resin was dewatered by centrifugal separation and dried under an air stream at 40 to 50 ° C. The total amount of foaming agent with which the resin was thereby impregnated was 11.8% by weight. 55% Expandable resin compositions were prepared by adding 100 parts by weight of the above-mentioned copolymer resin impregnated with volatile foaming agents, 2 parts by weight of a tin-containing stabilizing agent and one part by weight of calcium oo stearate or without the addition of talcum (experiments other than experiment no. 62) in an amount as shown in table 6 below or a combination of 0.5 part of sodium hydrogen carbonate and 0.4 part of citric acid (experiment no. 62) as nucleating agent, 65 or used as a decomposable foaming agent and an acrylic resin as a foam conditioning agent, as indicated in Table 6.

642,985

The notations given in Table 6 for the decomposable foaming agents and acrylic resins are as follows:

AIBN: cc, a'-azobisisobutyronitrile

PTS: p-toluenesulfonyl hydrazide

OBS: 4,4'-oxy-bis (benzenesulfonylyhydrazide)

DNM: dinitrosopentamethylene tetramine

Celmic 133: see example 4

E-3: A copolymer resin consisting of 80% by weight methyl methacrylate, 10% by weight butyl acrylate and 10% by weight ethyl acrylate with an intrinsic viscosity of 5.5 dl / g at 25 ° C.

E-4: A copolymer resin consisting of 85% by weight methyl methacrylate and 15% by weight butyl acrylate with an intrinsic viscosity of 5.0 dl / g at 25 ° C.

E-5: A commercially available acrylic resin, available under the trade name Paraloid K-125 from Rohm & Haas Co.

E-6: A commercially available acrylic resin, available under the trade name Paraloid K-125 from Rohm & Haas Co.

Each of these resin compositions was made into molded articles in the form of sheets by extrusion molding with the same extruder

used as in Example 3 and also used the same working conditions, and the foamed moldings were examined for the bulk density, the cell structure, the appearance, the compression strength and other mechanical properties, and for the thermal conductivity. The determination of the compressive strength was determined in accordance with the procedure as defined in ASTM D 1621 and the thermal conductivity was determined in accordance with the procedure as shown in the JIS under the designation A 1413. The results are summarized in Table 6.

In experiments Nos. 70 and 71, premature foaming of the resin composition was found while it was still in the nozzle, which resulted in broken foam bodies and the appearance of flow marks from the surfaces of the foamed moldings. The appearance of the foamed molded articles obtained in Experiment 69 was also unsatisfactory. The cell structure of the foamed molded article 20 was satisfactorily good in all experiments with the exception of the foamed molded article in experiment number 68, which showed less uniformity of the cell structure.

Table 6-1

Experiment no.

58

59

60

61

62

Nucleating agents,

Parts

1.0

1.0

1.0

1.0

(see text)

decomposable foaming

AIBN

PTS

OBS

DNM

Celmic

medium (parts)

(1.0)

(1.0)

1.0)

(1.0)

133

4 *

(1.0)

urea

(1.0)

Acrylic resin (parts)

E-3

meta-

E-4

E-5

E-5

(5.0)

blen

(5.0)

(1.0)

(20)

P 501

(5.0)

properties

Bulk density

0.033

of foamed g / ml

0.034

0.035

0.035

0.030

th shaped body

Compression

3.4

strength kg / cm2

3.3

3.5

3.5

3.0

Resistant to bending

speed, kg / cm2

5.1

5.4

5.4

4.8

5.3

Tensile strenght,

kg / cm2

5.0

5.2

5.3

4.8

5.1

Thermal conductivity

ability,

kcal / m / h ° C

0.025

0.026

0.026

0.025

0.028

Table 6-2

63

64

65

66

67

68

69

70

71

1.0

0.02

15

1.0

1.0

0.005

30th

1.0

1.0

AIBN

none none

Celmic

Celmic none none

Celmic

Celmic

(1.0)

133

133

133

133

(0.5)

(4.0)

(8.0)

(1.0)

E-5

E-5

E-5

E-6

E-6

E-3

E-3

E-3

E-3

(30)

(10)

(25)

(10)

(10)

(5.0)

(5.0)

(5.0)

(0.3)

0.035

0.034

0.040

0.033

0.045

0.070

0.059

0.080

0.095

3.8

3.6

4.8

3.3

5.0

7.3

6.0

7.3

12.4

6.7

6.5

7.8

5.5

8.1

10.3

8.8

13.0

20.1

5.5

5.4

7.0

5.3

7.8

10.5

9.0

16.8

21.3

0.028

0.027

0.029

0.028

0.031

0.037

0.035

0.038

0.043

13

642,985

Example 7 (Experiments Nos. 72 to 92)

In an autoclave with a capacity of 5 liters, which was made of stainless steel and equipped with a stirrer, 1000 g of a homopolymer-polyvinyl chloride resin or a copolymer resin consisting of vinyl chloride and vinyl acetate in the amounts shown in table 7, 2,000 g of purified water and one or a combination of two volatile foaming agents, as indicated in the table, in the amounts as also indicated in the table, if necessary, if necessary, filled in under pressure and then at 70 ° C stirred for 8 hours to impregnate the resin with the volatile foaming agents. After the impregnation was completed and cooled to room temperature and the excess foaming agent removed, the resin was dewatered by filtration and dried under an air stream at 40 to 50 ° C for about 5 hours. The resins so obtained

Screw diameter

Screw length

Compression ratio of the screw

jet

Sieves

Temperature of the cylinder

Temperature of the nozzle rotation speed

The shaped bodies obtained in this way were assessed with regard to the bulk density and the quality of the cell structure, whereby the data compiled in Table 7 were obtained.

For the notations of volatilizable and decomposable foaming agents, see the previous examples.

were evaluated for the amount of the foaming agent contained, and the data shown in Table 7 were obtained. In addition, the resins were left at 20 ° C for 1 week to determine the diffusion losses 5 during storage. The decrease in the amount of the foaming agent was in the range of 6 to 9% for all of the resins.

Foamable resin compositions were prepared by impregnating 100 parts of the resins obtained above, lowelche with volatile foaming agents, two parts of a tin-containing stabilizing agent and one part of calcium stearate together or without the addition of a nucleating agent, a decomposable foaming agent. and an acrylic resin (E-1) as a foam conditioning agent as shown in Table 7 below, and the resin compositions were made into foamed molded articles having the shape of cylindrical rods by using extrusion molding. The operating conditions of the extruder were as follows:

25 mm 750 mm

3.0

8 mm of the opening and

100 mm nozzle length one with 80 mesh openings and one with 100 mesh openings

Q = 60 to 120 "C

C, = 100 to 160 ° C

C3 = 120 to 180 "C

100 to 130 ° C

50 revolutions per minute

The criteria for cell structure A and B are given in Example 4 and cell structure C indicates that the cells of the foams had a diameter that was over one millimeter long and the structure was coarse and not uniform.

The foamed molded article obtained in Experiment No. 87 was clearly brittle and the foamed molded article from Experiments 91 and 92 showed significant shrinkage after molding.

35

40

Table 7-1

Experiment no.

72

73

74

75

76

77

PVC

Content of

Vinyl acetate% by weight

5

10th

0

10th

10th

10th

resin

P

400

750

750

1000

1000

1000

Vp, ml / g

0.011

0.013

0.060

0.025

0.025

0.025

volatilizable

TCFM

TCFM

TCFM

TCFM

TCFM

TCFM

Foaming agent

(150)

(150)

(150)

(150)

(150)

(150)

the applied

+

+

+

+

+

+

were (g)

BU

BU

BU

BU

BU

BU

(100)

(100)

(100)

(100)

(100)

(100)

Impregnation with

Foaming agent,% by weight

11.0

10.8

7.8

9.7

9.7

9.7

Nucleating agents

Tale

Tale

Tale

Hakuenka

Orben

Tale

(Parts)

(1.0)

(1.0)

(1.0)

(1.5)

(5)

(0.5)

decomposable

none

Celmic

PTS

AIBN

SHC

SHC *

Foaming agent

133

(0.03)

(0.5)

(0.5)

(2)

(Parts)

(1.0)

Acrylic resin

(E-l), parts

10th

10th

10th

10th

10th

10th

foamed

Bulk

Molded body density, g / ml

0.065

0.045

0.060

0.054

0.052

0.053

Cell structure

A

A

A

A

A

A

*) Sodium hydrogen carbonate

642 985 14

Table 7-2

78

79

80

81

82

83

84

85

86

10th

35

10th

10th

10th

10th

10th

10th

10th

1000

1700

850

850

850

850

850

850

850

0.025

0.029

0.015

0.015

0.015

0.015

0.015

0.015

0.015

TCFM

TCFM

PR

BU

PE

TCFM

TCFM

TCFM

TCFM

(150)

(150)

(300)

(300)

(300)

(300)

(300)

(100)

(200)

+

+

+

+

+

BU

BU

BU

BU

BU

(100)

(100)

(300)

(100)

(400)

9.7

9.3

6.5

7.5

8.3

15.6

3.4

8.6

15.0

Tale

Tale

Tale

Tale

Tale

Tale

Tale

Tale

Tale

(0.05)

(1.0)

(0.5)

(0.5)

(1.0)

(1.0)

(1.0)

(1.0)

(1.0)

SHC

none none none

Celmic

Celmic

Celmic

Celmic

Celmic

(5)

133

133

133

133

133

(2.0)

(0.5)

(0.5)

(0.5)

(0.5)

10th

10th

10th

10th

5

5

5

5

5

0.046

0.068

0.080

0.071

0.085

0.058

0.090

0.069

0.045

A

A

A

A

A

A

A

A

A

Table 7-3

87

88

89

90

91

92

10th

10th

0

10th

10th

10th

290

• 800

1700

2100

850

850

0.015

0.030

0.25

0.12

0.015

0.015

TCFM

TCFM

TCFM

TCFM

TCDFE

ISO

(150)

(150)

(150)

(150)

(200)

(200)

+

+

+

+

BU

BU

BU

BU

(200)

(200)

(200)

(200)

9.0

7.8

2.7

3.5

10.3

7.6

Tale

Tale none none

Tale

Tale

(0.01)

(1.0)

(1.0)

1.0)

none none

AIBN

none

Celmic

Celmic

(1.0)

133

133

(0.5)

(0.5)

0

0

0

10th

0

0

0.15

0.25

1.1

1.1

0.78

0.93

B

B

C.

C.

C.

C.

Example 8

(Experiments No. 96 to 109)

In a stainless steel autoclave with a capacity of 100 liters, which was equipped with a stirrer, 30 kg of a copolymer resin consisting of 90 wt .-% vinyl chloride and 10 wt .-% vinyl acetate with an average degree of polymerization of 1050 and a pore volume of 0.023 ml / g, 50 kg of purified water, 15 g of a partially saponified polyvinyl alcohol and 6 kg of trichlorofluoromethane and further 3 kg of butane were introduced under pressure, and the mixture was then stirred at 70 ° C. for 8 hours to the resin with trichlorofluoromethane and Impregnate butane as a volatile foaming agent. After the impregnation, cooling to room temperature and removal of the excess foaming agents, the resin was dewatered by centrifugation and dried under an air stream at 40 to 50 ° C. The total amount of trichlorofluoromethane and butane in the resin thus impregnated was 12.0% by weight.

Foamable resin compositions were prepared by adding 100 parts of the resin prepared above, which was impregnated with volatile foaming agents, two parts of a tin-containing stabilizing agent and one part by weight of calcium stearate together with or without the addition of one part of Tale as a nucleating agent, 0.5 Parts of Celmic 133 as a decomposable foaming agent and one of the acrylic resins E-7 to E-13 as shown in Table 8 below were mixed together and the resin compositions thus prepared were processed into foamed bodies which were in the form of sheets by an extruder was used which was kept under the operating conditions described below.

The nucleating agent was omitted in Experiment Nos. 106 and 107, and the decomposable foaming agent was omitted in Experiment Nos. 106 and 102.

Acrylic resins:

6o E-7: A copolymer resin consisting of 90% by weight methyl methacrylate and 10% by weight ethyl acrylate with an intrinsic viscosity of 4.5 dl / g at 25 ° C.

E-8: A copolymer resin consisting of 90% by weight of methyl methacrylate and 10% by weight of ethyl acrylate with an intrinsic viscosity of 7.0 dl / g at 25 ° C.

E-9: A copolymer resin consisting of 90% by weight of methyl methacrylate and 10% by weight of ethyl acrylate with an intrinsic viscosity of 11.0 dl / g at 25 ° C.

15

642,985

E-10: A copolymer resin consisting of 90% by weight of methyl methacrylate and 10% by weight of ethyl acrylate with an intrinsic viscosity of 15.3 dl / g at 25 ° C.

E-1: A copolymer resin consisting of 95% by weight of methyl methacrylate and 5% by weight of butyl acrylate with a basic viscosity of 10.7 dl / g at 25 ° C.

E-l2: A copolymer resin consisting of 80% by weight methyl methacrylate, 5% by weight ethyl acrylate, 5% by weight butyl acrylate and 10% by weight butyl methacrylate with an intrinsic viscosity of 10.0 dl / g at 25 ° C.

E-13: A copolymer resin consisting of 80% by weight of methyl methacrylate and 20% by weight of ethyl acrylate with an intrinsic viscosity of 2.0 dl / g at 25 ° C.

The operating conditions for the extruder were as follows:

Screw diameter 65 mm, screw length 1950 mm

Compression ratio of the screw 3.0

Jet:

Sieves:

Temperature of the cylinder

Temperature of the nozzle rotation speed

100 mm wide and 8 mm high one with 80 mesh openings and one with 100 mesh openings C] = 95 ° C C2 = 130 ° C C3 = 150 ° C 120 ° C

20 revolutions / minute

The resulting foamed molded article was evaluated for the bulk density, the cell structure, the compression strength, determined in accordance with ASTM method D 1621 and the flexural strength, in accordance with the procedure ISO R 1209 s, whereby the results which are summarized in Table 8 were obtained.

In experiments 104 and 105, a premature foaming of the resin composition was found, which took place while it was still in the nozzle, io whereby broken foams were obtained to a large extent, and shrinkage of the foamed molded body occurred after shaping and a less uniform cell structure . The foamed molded articles obtained in Experiments No. 108 and 109 were also less uniform in cell structure, although there was no premature foaming of the resin composition.

As can be seen from the data compiled in the table, acrylic resins with a higher basic viscosity can give advantages, e.g. a possible reduction in the amount of acrylic resin, as well as an improved retention of the gas, which leads to the formation of foam, and to stabilize the foam cells and reduce the shrinkage. On the other hand, if the acrylic resin used has a low intrinsic viscosity or if the amount of acrylic resin used is insufficient, the foams are broken to a large extent and this leads to a large shrinkage of the foams after shaping and to a coarser cell structure of the 30 foams.

Table 8-1

Experiment No.

96

97

98

99

100

101

Acrylic resin,

E-7

E-8

E-9

E-1 1

E-12

E-10

(Parts)

(10)

(6)

(5)

(6)

(6)

(2)

properties

Bulk density

0.049

0.067

of the g / ml

0.048

0.048

0.043

0.050

foamed

Cell structure

A

A

A

A

A

A

Molded body

Compression

4.5

4.4

6.3

strength kg / cm2

3.4

3.4

3.0

Resistant to bending

6.0

9.3

kg / cm2

5.7

5.6

5.0

6.3

Table 8-2

102 103

104

105

106

107

108

109

E-10 E-10

E-10

E-13

E-7

E-7

no

no

(5) (25)

(0.3)

(5)

(10)

(10)

0.042 0.050

0.23

0.25

0.12

0.095

0.16

0.15

A A

B

B

B

B

C.

C.

3.0 3.6

21.0

22.3

-

-

-

-

5.1 6.5

29.3

April 30

-

-

-

-

Impregnate Example 9 55. After the impregnation and cooling (Experiments No. llO to No. 117) were completed, the excess was removed in a stainless steel autoclave with a chamfer foaming agent, and the resin was removed by a 10 liter filter with a stirrer. dehydrated and dried under an air flow, 3 kg of a homopolymer vinyl chloride were at 50 ° C for 5 hours. The total amount of the resin or a copolymer resin of vinyl chloride 6Qmungsmittel in the resins impregnated in this way is in the Ta and vinyl acetate, the vinyl acetate content of the resin in belle.

in the following table, filled with a foamable resin composition having an average degree of polymerization and a pore volume, in each case by adding 100 parts by weight of the above-obtained, as indicated in the table, 5 kg nectified water impregnated with volatile foaming agents, 1.5 g of a partially saponified polyvinyl alcohol 65 resin, 2 parts by weight of a tin-containing stabilizing agent and 600 g of trichlorofluoromethane and further 300 g of butane by means of 1 part by weight of calcium stearate and one part of Tale filled as a germ under pressure and then was stirred for 8 educational agents and 10 parts of one of the acrylic resins, E-7, E-10 hours at 70 ° C to methane the resin with trichlorofluoro- and E-13 (see Example 8) and foam conditioning agent Butane as a volatile foaming agent to be mixed together, and the resin composition

642,985

16

was processed into foamed moldings which have the greater degree of polymerization, the uses

Had the shape of cylindrical rods, in which case one proceeded in the direction of an acrylic resin with a correspondingly higher manner as in Example 7. The bulk density and the basic viscosity desired, and foam body with a high

Properties of the cell structure of this foamed molded article with a uniform cell structure can be shown in Table 9. The foamed molds 5 are obtained even with resins having a small content of vinyl acetate, which was obtained in experiments 115 and 116, and which otherwise had a relatively high temperature, showed a slight shrinkage after molding. would need to manufacture by using the acrylic resin

As can be seen from the data given in Table 9 - appropriately borrowed as a foam conditioner - in the event that the vinyl chloride-based resins are selected.

Table 9

Experiment no.

110

111

112

113

114

115

116

117

PVC

Vinyl content

Resin acetate, wt .-%

5

5

10th

0

10th

10th

0

0

P

700

1050

1500

850

510

1500

850

850

Vp, ml / g

0.021

0.025

0.033

0.038

0.019

0.033

0.038

0.038

Acrylic resin (parts)

E-10

E-10

E-10

E-10

E-7

E-7

E-7

E-7

(10)

(10)

(10)

(10)

(10)

(10)

(10)

(10)

foamed

Bulk density,

Shaped body g / ml

0.048

0.051

0.066

0.060

0.040

0.081

0.093

0.25

Cell structure

A

A

A

A

A

A (* l)

A

B

Example 10 25 Next, foamable resin compositions (Experiments No. 118 to No. 133) tongues were prepared by mixing 100 parts each of the above in a 5 liter stainless steel autoclave with foaming agent impregnated with foaming agents, 2 solvents, which was equipped with a stirrer, parts of a tin-containing stabilizing agent and one were 1000 g of homopolymeric polyvinyl chloride resin or part of calcium stearate together or without the addition of germs in a copolymer resin of vinyl chloride and vinyl acetate, thus forming agents of the type given in Table 10, and the content of vinyl acetate in Table 10 below, in an amount as also indicated in the table, with an average degree of polymerization of a decomposable foaming agent, as well as the pore volume and a pore volume as given in the table in the table and a copolymer resin Sl, consisting of 2000 g cleaned es water, 1.0 g of partially saponified polyvinyl from 70% by weight of styrene and 30% by weight of acrylonitrile with an alcohol and 150 g of trichlorofluoromethane and a further 100 g of 35 basic viscosity of 12.0 dl / g at 25 ° C. as a foam conditioner butane The pressure was charged, and then the styrene-based detergent was mixed in an amount as stirred at 70 ° C for 8 hours around the resin shown in the trichlor table, and the resin fluoromethane and butane were made into volatile foaming agent compositions to impregnate into foam bodies in the form of tel. After the impregnation and cylindrical rods had been finished by extrusion molding and cooling to room temperature, the excess 40 tet was. The operating conditions of the extruder were largely exfoliated, and the resin was dried by the same as in Example 7.

Filtration dewatered and dried in a stream of air at 40 to 50 ° C for about 5 hours. The foamed molded articles thus obtained were evaluated for the total amount of the foaming agent impregnated in terms of the bulk density and the cell structure, and the resin was determined, and the results are shown in Table 45, and the results as shown in Table 10 were obtained belle 10 stated. The loss of foaming agents through are.

Leakage during storage at 20 ° C for one week ranged from 6 to 9% for all of these resins.

Table 10-1

Experiment no.

118

119

120

121

122

123

PVC

Salary

resin

Vinyl acetate,

% By weight

5

10th

0

10th

10th

10th

P

400

750

750

1000

1000

1000

Vp, ml / g

0.011

0.013

0.060

0.025

0.025

0.025

impregnation

with volatilize

ed foaming

medium,% by weight

11.0

10.8

7.8

9.7

9.7

9.7

Nucleation

Tale

Tale

Tale

Tale

Tale

Orben tel (parts)

(2.0)

(1.0)

(1-0)

(0.03)

(0.5)

(5)

decomposable

Celmic

SHC

Celmic

AIBN

Foaming agent

none

133

none

(4.0)

133

(0.5)

(Parts)

(1.0)

(1.5)

17th

642,985

Table 1 (1-1 (continued) Experiment No.

Styrene-based resin (S-l),

Parts of foamed moldings

Bulk density g / ml cell structure

118

6.0

119

6.0

120

10.0

121

8.0

122

8.0

123

8.0

0.060 0.044 0.061 0.049 0.050 0.055 A A A A A A

table

10-2

124

125

127

128

129

130

131

132

10th

35

10th

10th

10th

0

10th

45

1000

1700

1000

1000

1000

1700

2100

1800

0.025

0.029

0.030

0.030

0.030

0.25

0.21

0.025

9.7

9.3

9.4

9.4

9.4

2.7

3.5

6.0

Haku

Talc

Talc none none none none

Tale enka

(1.0)

(1.0)

(1.0)

(20)

PTS

none none

AIBN

none none none none

(0.3)

(1.0)

8.0

10.0

none none

8th

none

8th

none

0.060

0.069 -

0.20

0.18

0.20

1.1

1.1

0.30

A

A

C.

C.

C.

C.

C.

B

Example 11 (Experiments No. 134 to No. 143)

In a stainless steel autoclave with a capacity of 5 liters, which was equipped with a stirrer, 1000 g of copolymer resin consisting of 90 wt .-% vinyl chloride and 10 wt .-% vinyl acetate with an average degree of polymerization of 950 and a pore volume of 0.015 ml / g, 2000 g of purified water and 1.0 g of partially saponified polyvinyl alcohol and one or a combination of types of volatile foaming agent were added or filled in under pressure, as indicated in Table 11 which follows, and the mixture was then stirred at 70 ° C for 8 hours to impregnate the resin with the foaming agent.

After the impregnation, cooling to room temperature and removal of the excess foaming agent, the resin was dewatered by centrifugation.

30 sert and dried under a stream of air. The amount of the foaming agent contained in the impregnated resin is shown in Table 11.

Foamable resin compositions were prepared by in each case mixing 100 parts of the 35 resin prepared above with the foaming agent with Tale as the nucleating agent, Celmic 133 as the decomposable foaming agent and the copolymer resin SI based on styrene as the foam conditioning agent in the amounts given in Table 11, and the resin composition was processed into foamed molded articles in the same manner as in the previous example. The bulk density of the moldings thus obtained is given in Table 11. The foamed moldings of experiments No. 141 and 142 showed a clear shrinkage after the shaping.

Tables

Experiment no.

134

135

136

137

138

139

140

141

142

143

volatilizable

PR

BU

PE

TCFM

TCFM

TCFM

TCFM

TCFE

ISO

TCFM

Foaming agent (g)

(300)

(300)

(300)

(300)

(30)

(100)

(200)

(200)

(8.4)

(30)

+

+

+

BU

BU

BU

(30)

(100)

(400)

Impregnation with

Foaming agent,

% By weight

6.5

7.5

8.4

15.6

3.5

8.9

14.0

11.0

8.4

1.5

Tale, parts

1.0

1.0

2.0

2.0

2.0

2.0

2.0

1.0

1.0

1.0

Celmic 133, parts

0

0

1.0

1.0

0.5

0.5

0.5

0.5

0.5

0

Resin (S-l)

Styrene base, parts

5

5

5

5

5

5

5

0

0

0

Bulk density of

foamed molding

pers, g / ml

0.075

0.064

0.084

0.052

0.088

0.068

0.041

0.79

0.94

0.77

642,985

18th

Example 12 in the amounts given in Table 12

(Experiments No. 144 to No. 150) mixed together, and the resin composites

30 kg of a copolymer resin was best used in an autoclave made of stainless steel with a capacity for foamed moldings in the form of sheets with a capacity of 100 liters, which was worked out with a stirrer using extrusion molding of an extruder that works with the same

Working from 90% by weight of vinyl chloride and 10% by weight of vinyl coating conditions, as in Example 8.

did with an average degree of polymerization of

1050 and a pore volume of 0.023 ml / g, 50 kg sufficient in terms of bulk density, cell structure, compression

pure water, 15 g of partially saponified poly vinyl alcohol and strength and flexural strength were assessed and the

6 kg trichlorofluoromethane and a further 3 kg butane, under loResultate, as they are summarized in Table 12. In

The pressure was filled in and then an early application was carried out at 70 ° C. during experiments 149 and 150.

Stirred for 8 hours to detect the resin with trichlorofluoromethane foaming of the resin composition, while and butane as a volatile foaming agent was still present in the nozzle, resulting in broken gnomes. After completion of the impregnation, cooling on foams resulted in significant shrinkage of the

Room temperature and removal of the excess foams after the molding showed

The resin was dewatered using abzen-styrene-based copolymer resins:

centrifuged and dried under an air stream at 40 S-2: a copolymer resin consisting of 70 wt .-% styrene to 50 ° C. The total amount of the foaming agent in the and 30 wt .-% acrylonitrile with an intrinsic viscosity of impregnated resin, which was prepared, was 12.0 2.0 dl / g at 25 ° C.

% By weight. 20 S-3: a copolymer resin consisting of 70% by weight styrene

Foamable resin compositions were prepared and 30% by weight of acrylonitrile with an intrinsic viscosity of by in each case 100 parts of the Co 4.0 dl / g obtained above at 25 ° C.

polymer resin, which was impregnated with foaming agent, 2 S-4: a copolymer resin consisting of 70 wt .-% styrene

Parts of a tin-containing stabilizer, part and 30% by weight of acrylonitrile with an intrinsic viscosity of

Calcium stearate, a part of Tale as a nucleating agent, 0.5 2510.0 dl / g at 25 ° C.

Parts of Celmic 133 as a decomposable foaming agent and S-5: a copolymer resin consisting of 75% by weight of styrene and part of copolymer resins S-2 to S-5 based on styrene, such as those and 25% by weight of acrylonitrile with an intrinsic viscosity of further 14.6 dl / g at 25 ° C are described in more detail below as foam condition.

Table 12

Experiment no.

144

145

146

147

148

149

150

Resin on styrene

S-3

S-4

S-4

S-4

S-5

S-2

S-4

base (parts)

(8.0)

(2.0)

(5.0)

(25.0)

(5.0)

(5.0)

(0.3)

Own

Bulk density

g / ml

0.045

0.059

0.044

0.053

0.042

0.16

0.19

of the ge

Cell

foamed structure

A

A

A

A

A

C.

C.

Molded body

Compression

strength

kg / cm2

2.9

3.9

2.9

3.3

2.6

22.4

April 28

Resistant to bending

speed

kg / cm2

7.4

10.3

7.3

8.6

6.6

31.6

12.4

As can be seen from the results shown in Table 12 and the degree of pore volume, which can be seen in the table, styrene-based copolymer resins with 1, 5 kg of purified water, 1.5 g of a partially saponified, larger basic viscosity than foam conditioning Polyvinyl alcohol and 600 g trichlorofluoromethane

medium brings the advantages of improved gas retention or 50 and finally 200 g of butane were introduced under pressure

Foam formation, stabilization of the foam and reduced and then was carried out at 70 ° C for 8 hours

ter shrinkage even if the amount of resin that agitates the resin with trichlorofluoromethane and Bu-

is added, is relatively small, while impregnating the users as volatile foaming agents,

A resin with a lower basic viscosity is added. After the impregnation has been completed, it is cooled to room temperature.

broken foams and increased shrinkage after 55 temperature and deduction of excess foaming

the shape, resulting in a coarser cell structure, the resin was dewatered by filtration and obtained, especially when the amount of addition dried under an air stream at 50 ° C for 5 hours

is not sufficient. the. The total amount of the foaming agents in the impregnated resins was as shown in Table 13.

Example 13 60 Foamable resin compositions were prepared.

(Experiments Nos. 151 to 156) by adding 100 parts each of the above

In an autoclave made of stainless steel, resin impregnated with a volatile foaming agent,

capacity of 10 liters, which was equipped with a stirrer consisting of 2 parts of a tin-containing stabilizing agent, 3 kg of homopolymeric polyvinyl chloride part of calcium stearate, part of Tale as nucleating agent,

resin or a copolymer resin of vinyl chloride and vinyl acetate 65 0.5 parts of Celmic 133 as a decomposable foaming agent and did, the vinyl acetate content in Table 13 further being a styrene-based resin of the type indicated in the table.

below, with an average polymer, as a foam conditioning agent in an amount as they are

19th

642,985

is also given in the table, with each other with a uniform cell structure can be obtained

mixed, and the resin compositions were prepared by Ex- even with vinyl chloride-based resins without Vinylace-

trusion molding into foamed moldings is present in the glide or even with only a slight vinyl

Chen way as processed in Example 10. The bulk density factual content, which on the other hand is a relatively high manufac

and the condition of the cell structure of this foamed molding temperature and a suitable selection of the body are given in Table 13. The foamed foam conditioning agent.

Shaped bodies in experiment 155 showed shrinkage on the other hand, a copolymer resin, which has a certain degree of shape and a significantly low degree of polymerization, can

brittleness of the foams encountered in the experiment no. give molded articles of high foaming,

156, which causes shrinkage of the foamed molded articles even when a styrene-based resin is used as a foam

after the shaping occurred to a large extent. Resource is applied, which is a relatively low

As it has basic viscosity from the results shown in Table 13, and if the content of vinyl

as can be seen, the styrene-based resin should be large as a foam compound in the copolymer resin, but a foamed ditioning agent may desirably have a higher basic viscosity molded article with a high foaming ratio only if the vinyl chloride-based resin 15 is difficult to obtain if to be a copoly

has a relatively high degree of polymerization. A resin is used in which the vinyl acetate content is low-foamed molded body with a high degree of foaming.

Table 13

Experiment no.

151

152

153

154

155

156

PVC

Content of

resin

Vinyl acetate,

% By weight

5

10th

0

10th

10th

0

P

700

1500

750

800

1500

850

Vp, ml / g

0.021

0.033

0.037

0.021

0.033

0.03Ì

Impregnation with

Foaming agent,

% By weight

11.5

10.5

10.1

11.5

10.5

10.0

Resin on styrene

S-5

S-5

S-5

S-3

S-3

S-2

base (parts)

(6)

(10)

(10)

(10)

(10)

(10)

Foaming

Bulk density,

form g / ml

0.043

0.059

0.055

0.050

0.073

0.15

body

Cell structure

A

A

A

A

A

C.