CN1086225A - Method for preparing decomposable film and its application - Google Patents

Abstract

A method for preparing a decomposable film, which comprises the poly-alpha-formaldehyde Styrene or polyalkylene carbonate dispersed in water, or preferably poly α-methylstyrene or polyalkylene carbonate is dissolved in a solvent, and the raw The resulting solution is dispersed in water, and the solvent is evaporated so that the solvent content can be In the range of 20 to 100% by weight (as poly-alpha-methylstyrene or based on the weight of the polyalkylene ester), the resulting aqueous emulsion is applied, and then the step of post-drying the emulsion; and the step of preparing a metal film with a flat surface One method involves depositing a metal on the surface of a decomposable film, and then followed by the step of treating the film at a temperature above the decomposition temperature.

Description

The present invention relates to a method for preparing a decomposable polymer film and its application, in particular to a method for preparing a decomposable film by coating an emulsion containing a specific polymer, and its application.

It has been widely practiced that, in order to temporarily smooth a rough surface or temporarily protect a surface, a solution of a decomposable polymer is applied and then dried to form a coating film. In this case, the decomposable polymer (when used) is usually dissolved in an organic solvent, but in this case it is not desirable to use an organic solvent, preferring to use an aqueous emulsion. For this purpose, aqueous emulsions obtained by emulsion polymerization of methacrylates have been used.

The aqueous emulsion of polymethacrylate has quite good thermal decomposition properties, but it is difficult to completely decompose and gasify the aqueous emulsion of polymethacrylate under anaerobic or anhydrous conditions, even when heated. Therefore, this conventional technique has a problem of leaving a large amount of undecomposed residues, and thus it is required to develop a polymer emulsion having excellent decomposing properties.

In order to solve the above-mentioned problems, the present inventors have intensively studied an aqueous polymer emulsion having more excellent decomposition properties, and as a result, have accomplished the present invention.

It is an object of the present invention to provide a method for producing disintegrated films comprising the steps of applying and subsequently drying an aqueous emulsion in which poly-alpha-methylstyrene or polyalkylene carbonate polymers are dispersed in water.

Another object of the present invention is to provide a use of the thus obtained decomposable film, in which there is a method for preparing a metal film with a flat surface, which comprises the process of forming a metal film made of poly-α-methylstyrene or The aqueous emulsion obtained by dispersing polyalkylene carbonate in water is applied to the rough surface, and then the emulsion is dried; the metal is deposited on the surface of the formed poly-alpha-methylstyrene or polymethylene carbonate coating, The coating is then treated at a temperature above the thermal decomposition temperature of the polyalpha-methylstyrene or polyalkylene carbonate.

According to the present invention, in the method of producing a decomposable film, the film can be easily produced without evaporating an organic solvent, and therefore, the present invention is industrially valuable. Thus, for example, the present invention is useful for forming thin films of deposited metals with smooth surfaces.

Polymers such as poly-α-methylstyrene, which can be prepared by anionic polymerization of α-methylstyrene, are used in the present invention. Copolymers of other styrene monomers can also be used as long as it does not lower the decomposition properties. For example, in the case of using styrene, its content is preferably in the range of 50 mol% or less. The number average molecular weight of the polymer is preferably in the range of about 5,000 to about 1,000,000. A particularly preferred polymer is poly-α-methylstyrene having a number-average molecular weight of 50,000 or less and a weight-average molecular weight/number-average molecular weight ratio of 3 or more. When this polymer is used, it is possible to obtain In addition to the above-mentioned anionic polymerization, poly-α-methylstyrene can also be prepared by cationic polymerization of α-methylstyrene with Lewis acid or the like without mixing polymers, and the obtained polymer can satisfy the above-mentioned need. For example, if cationic polymerization is carried out at relatively high catalyst concentrations and at relatively high temperatures, desired products can be obtained. On the other hand, polymers obtained by conventional anionic polymerization have a molecular weight distribution of at most 2 even when the polymerization is carried out at an elevated catalyst concentration, and thus the polymers thus obtained cannot satisfy the above requirements. Therefore, it is necessary to purify part of the catalyst in the polymerization process so that the polymerization is realized at a lower polymerization temperature, or the oligomers prepared by cationic polymerization are mixed with the polymers, so that the molecular weight distribution is broadened and the desired glass can be obtained A polymer having a transition temperature, especially a polymer having a glass transition temperature of 100°C or lower, especially 100-0°C, may preferably be used.

As for polyalkylene carbonate, an example of it can be prepared by copolymerizing alkylene oxide and carbon dioxide containing 2 to 10 carbon atoms in the presence of a catalyst, and the number average molecular weight of the applicable interpolymer is 1000-1000000 , usually around 5000-500000. The copolymer can be hydrolyzed with base to reduce its molecular weight before use. In addition, as polyalkylene carbonates, polycarbonates prepared from diols and 2,5-dialkyl-O-O'-bis(1-imidazolylcarbonyl)-2,5-hexanediol are also available [ Houlihan et al., Macromolecules, 19, P13 (1986)] and polymers prepared by ring-opening polymerization of cyclic carbonates [Keul et al., Makromol.chem., 187 P2579 (1986); and Storeg et al., Macromolecules, 25, P5369 (1992)].

In the present invention, the above polymer is dissolved in a relatively high concentration in a solvent such as benzene, toluene, xylene, ethylbenzene, dichloroethane, chloroform or dichloroethane, which are immiscible with water. The resulting solution is mixed with water containing a small amount of surfactant and a water-soluble polymer under fairly vigorous stirring, thereby achieving emulsification. The emulsion thus prepared was heated under reduced pressure with stirring to remove the solvent, thereby preparing an aqueous emulsion. Solvent removal does not have to be complete, and when a certain amount of solvent remains, the resulting film may have excellent properties. For this purpose, the amount of solvent is in the range of 20-100% by weight based on the weight of the polymer. In this case, it is preferable to use a plasticizer in order to adjust the viscosity of the polymer solution. As plasticizers, preference is given to using compounds with low melting points and rather high boiling points. Examples of usable plasticizers include phthalates, phosphates and oligomers of α-methylstyrene, in which case it is sometimes not always necessary to retain the solvent. Especially when fatty carboxylate is used, the viscosity of the emulsion is low, and the fluidity of the emulsion can be maintained even if the polymer concentration is increased. Since film formation can be achieved by using concentrated emulsions, good films are finally produced. Typical examples of aliphatic carboxylic acid esters include esters of divalent carboxylic acids such as adipic acid, azelaic acid and sebacic acid, and Esters of monovalent carboxylic acids such as oleic acid. For the formation of these esters, alcohols with 3 or more carbon atoms are preferably used. In addition, for the stabilization of aqueous emulsions, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium phosphate, sodium dihydrogen phosphate, potassium phosphate and diphosphate Potassium Hydrogen.

Emulsification can also be achieved by other methods, such as by first dissolving the above polymer in a solvent at a relatively high concentration to be mixed with water, and then mixing the solution with water containing a small amount of anionic or nonionic surfactant and water under vigorous stirring. Water mixing of non-volatile polymers. In this case, after emulsification, if necessary, excess solvent is removed by heating under reduced pressure with stirring.

In order to form a uniform film with good properties from the emulsion, a defoamer may be used, and the kind of defoamer used for this purpose is not particularly limited, and various types of commercial silicon-based defoamers may be used. The amount of the antifoaming agent used is in the range of 1/100000 to 1/1000 of the emulsion.

As antifoaming agents, various types of products are commercially available and utilized. Silicone-based defoamers, in particular, are effective and easy to use.

The concentration of the polymer in the emulsion here is usually 5% by weight or more, preferably 10 to 30% by weight. As surfactants are mainly nonionic, anionic and cationic products on the market, any type of these surfactants may be used, but anionic and nonionic surfactants may be particularly preferably used. Examples of surfactants include carboxylates, sulfonates, sulfates, phosphates, quaternary ammonium salts, ethers, ether esters, esters and fatty amides. Typical examples of these surfactants include sodium alkylbenzene sulfonate, sodium alkyl sulfonate, polyalkylene oxide alkyl ether, polyalkylene oxide alkyl phenyl ether, polyalkylene oxide alkyl ether sulfonate and Polyoxyalkylene ether phosphate.

Examples of water-soluble polymers that can be used for stabilizing the emulsion include polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyN-methylpyrrolidone and polypyridine.

In the present invention, the emulsion thus obtained is coated and then dried to form a decomposable film, but the drying is carried out at a temperature not higher than the decomposition temperature of the polymer, ie, usually in the range of 50 to 200°C.

The film thus produced can be heated at a temperature ranging from 250 to 500°C so that the film can be completely vaporized. Thus, the film is removed at relatively low temperatures, for which reason, for example, the film applied to the substrate has no problem of deterioration.

In actual use, applying the decomposable film on the shell can form a flat metal film on the rough surface. In fact, a metal film can be formed on a decomposable film by vapor deposition, and then heated to vaporize/remove the decomposable film, so that a flat metal film can be formed on a rough surface.

That is, the emulsion obtained as described above can be applied on a rough surface to form a smooth metal film on the surface, and then dry the smooth surface. Next, the metal is deposited on the smooth surface and then heated at a temperature higher than the decomposition temperature of the polymer, thereby forming a metal film with a flat surface. There is no particular limitation on which metal is used as long as it can be deposited, but examples of generally usable metals include gold, silver, aluminum, nickel and copper. The above-mentioned drying is performed at a temperature lower than the decomposition temperature of the polymer, usually at 50 to 200°C. The deposition of the metal is likewise carried out at a temperature below the decomposition temperature of the polymer, usually at a temperature of 50 to 100°C, and the decomposition of the polymer at a temperature of 200 to 500°C. Therefore, the thin film is removed at a low temperature, and therefore, there is no problem of deterioration and deformation of the metal.

Now, the present invention will be described in detail with reference to Examples, and the scope of the present invention should not be limited by these Examples.

Example 1

In 20 milliliters of benzene, dissolve 8 grams of α-methylstyrene trimer and 12 grams of polyα-methylstyrene with a number average molecular weight of 120,000 (it is produced by polymerizing α-methylstyrene in the presence of butyllithium styrene), and this solution was added to an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 ml of water. Next, thorough mixing was performed using a homogenizer, and then 18 ml of benzene was distilled off with stirring under a reduced pressure of 100 mmHg. The emulsion thus prepared was coated on a glass plate and dried to form a 3 micron thick film. Thereafter, the film was treated at 380°C for 1 hour, as a result of which the film was completely vaporized.

Comparative example 1

Carry out by the same procedure of embodiment 1, difference is that the emulsion is prepared by emulsion polymerization of methyl methacrylate in the presence of potassium persulfate (a surfactant, the solid concentration is the same as in embodiment 1), and at this In both cases, char residues were observed on the glass surface.

Example 2

The same procedure as in Example 1 was carried out except that 20 g of oligomer (number average molecular weight = about 4500) was used which was prepared by hydrolysis of polypropylene carbonate (number average molecular weight = about 80000) with aqueous sodium hydroxide solution . The polypropylene carbonate is produced by polymerizing propylene oxide and carbon dioxide. In this case, no residue was observed at all.

Example 3

The same procedure as in Example 1 was carried out, except that sodium dodecylbenzenesulfonate was replaced with polyethylene glycol nonylphenyl ether, so that a film of 4 micrometers was formed. Next, the film was treated at 380°C for 1 hour, as a result of which the film was completely vaporized.

Example 4

Dissolve 8 g of α-methylstyrene trimer and 12 g of poly-α-methylstyrene with a number average molecular weight of 120,000 in 20 g of toluene, which is polymerized α-methylstyrene in the presence of butyllithium And made. The solution was then added to an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 ml of water. Next, thorough mixing was performed with a homogenizer, and 15 g of toluene was distilled off with stirring under a reduced pressure of 100 mmHg. The emulsion thus prepared was coated on a glass plate and dried to form a 3 micron thick film. The film thus formed had a flat surface, and this film was then treated at 380° C. for 1 hour. As a result, the film was completely vaporized. On the contrary, when 19 grams of toluene was removed, the resulting film was not completely flat, and a roughness of about 0.3 microns was observed.

Example 5

The same procedure as in Example 4 was carried out, except that 20 g of oligomer (number average molecular weight = about 4500) was used, which was prepared by hydrolyzing polypropylene carbonate (number average molecular weight = about 80000) with aqueous sodium hydroxide solution. Well, the latter is produced by polymerizing propylene oxide and carbon dioxide. 30 g of methyl ethyl ketone was used as a solvent, and 20 g of methyl ethyl ketone was removed. In this case, the surface of the produced film was smooth and no residue was observed at all.

Example 6

In 20 g of toluene were dissolved 8 g of diisobutyl adipate and 12 g of poly-alpha-methylstyrene with a number average molecular weight of 12,000 and a weight average molecular weight/number average molecular weight ratio of 6.5, the latter being polymerized by polymerization in the presence of sulfuric acid α-Methylstyrene and the system. The solution was then added to an aqueous solution obtained by dissolving 1 gram of sodium dodecylbenzenesulfonate in 100 milliliters of water, followed by thorough mixing with a homogenizer, and then stirring and heating the solution at 40° C. under a reduced pressure of 100 mmHg. The solution was distilled off with 15 g of toluene. In the emulsion thus obtained, the solid concentration (ratio of poly-α-methylstyrene and diisobutyl adipate to the total amount) was 35%. Thereafter, the emulsion was spin-coated at 100 rpm and then dried at 80°C to obtain a uniform transparent film with a thickness of 8 µm. Subsequently, the film was treated at 380°C for 1 hour, as a result, the film was completely vaporized.

Example 7

Carry out by the same procedure of embodiment 6, difference is to use the number-average molecular weight that is 120000 and the ratio of weight-average molecular weight/number-average molecular weight to be 1.8 poly-alpha-methylstyrene that the number average molecular weight that makes by anion polymerization is used, when solid concentration is 35 %, the rotation speed of spin coating is 400rpm and only a thick film with a thickness of 65 microns can be obtained. In addition, when diluted to 15% solids and coated, it is possible to obtain a film with an average thickness of 8 microns, but it must be whitened. Next, the film was treated at 380°C for 1 hour, as a result of which the film was completely vaporized.

Example 8

Carry out by the same procedure of embodiment 6, difference is to replace diisobutyl adipate with dioctyl phthalate, obtain the emulsion that solid concentration is 35%. When using this emulsion, a transparent film with a thickness of 10 microns was obtained. Thereafter, the film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 9

Carry out by the same procedure of example 6, difference is to use the poly-alpha-methylstyrene that the number average molecular weight is 120000 and weight average molecular weight/number average molecular weight ratio is 1.6 by anionic polymerization. In this case, a whitening film having a thickness of 9 µm was prepared, and subsequently, the film was treated at 380°C for 1 hour, as a result, the film was completely vaporized.

Example 10

In 20 grams of toluene, dissolve 8 grams of diisophenyl adipate and 12 grams of polymerized alpha-methylstyrene in the presence of butyl lithium to obtain polyalpha-methylstyrene with a number average molecular weight of 120,000, and then This solution was added to an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 g of water. Subsequently, thorough mixing was performed with a homogenizer, the solution was heated at 40°C with stirring under a reduced pressure of 100 mmHg, and 15 g of toluene was distilled off. The solid concentration (ratio of poly-α-methylstyrene and diisobutyl adipate to the total amount) in the thus prepared emulsion was 35%. Thereafter, the emulsion was spin-coated at 300 rpm, and then dried at 80° C. to obtain a uniform film with a thickness of 12 μm. The coated film was then treated at 380°C for 1 hour, as a result, the film was completely vaporized.

Example 11

Carry out by the same procedure of embodiment 10, differently replace gram 1 sodium dodecylbenzene sulfonate with 0.5 polyethylene glycol nonylphenyl ether and polyvinyl alcohol (saponification rate=85%, degree of polymerization=2000) at the same time, A film having a thickness of 13 microns was obtained, and subsequently, the film was treated at 380° C. for 1 hour, as a result, the film was completely vaporized.

Example 12

The same procedure as in Example 10 was carried out, except that diisobutyl phthalate was used instead of diisooctyl adipate. When the solid concentration was 35%, only a thick film with a thickness of 65 microns was produced. In addition, when the solid concentration was diluted to 20% and coated, a film with an average thickness of 15 microns was obtained, but it was somewhat uneven. Subsequently, the film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 13

Carry out by the same step of embodiment 10, difference is to replace di-iso-octyl adipate with di-iso-octyl phthalate, when solid concentration is 35%, only obtain the thick film that thickness is 70 microns, in addition, When diluted to 15% solids and coated, a film with an average thickness of 13 microns was obtained, but somewhat uneven. Subsequently, the film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 14

Proceed in the same manner as in Example 10, except that 20 grams of polypropylene carbonate (number average molecular weight = 80,000) is used instead of poly-alpha-methylstyrene, the former is obtained by polymerizing propylene oxide and carbon dioxide; acetic acid Ethyl ester was used as a solvent; 2-ethylhexyl adipate was used as a plasticizer to obtain an emulsion with a solids concentration of 38%. When using this emulsion, a homogeneous film with a thickness of 8 micrometers was obtained. Subsequently, the coated film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 15

Carry out by the same method of embodiment 2, difference is to replace 2-ethylhexyl adipate with dioctyl phthalate. When the solid concentration was 38%, only a thick film with a thickness of 45 micrometers was obtained; in addition, when the solid concentration was diluted to 16% and coated, a film with an average thickness of 10 micrometers was obtained, but not uniform. Subsequently, the film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 16

In 20 g of toluene, 20 g of poly-alpha-methylstyrene (trade name resin 18#120, manufactured by Amoco Chemicalls Co., Ltd.) with a glass transition temperature of 45°C was dissolved in 20 g of toluene, and the solution was then added to the In an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 ml of water. This is followed by thorough mixing with a homogenizer. The solution was heated at 40°C with stirring under a reduced pressure of 100 mmHg to distill 19 g of xylene. In the emulsion thus obtained, the solids concentration was 40%. Thereafter, the emulsion was spin-coated at 100 rpm, and then dried at 80° C. to obtain a uniform and homogeneous film with a thickness of 8 μm. Subsequently, the coated film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 17

The same procedure as in Example 1 was carried out, except that 1 gram of dodecylbenzenesulfonic acid was replaced with 0.5 gram of polyethylene glycol nonylphenyl ether and polyvinyl alcohol (saponification rate=85%, polymerization degree=2000) Sodium gave a film with a thickness of 10 microns. Subsequently, the coated film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 18

Carry out by the same procedure of embodiment 16, difference is that the number average molecular weight that uses 20 grams to make by anionic polymerization is 120000 and the ratio of weight average molecular weight/number average molecular weight is 1.8 poly-alpha-methylstyrene (glass transition complex temperature = 168°C). In this case, a whitening film having a thickness of 7 µm was obtained, and subsequently, the film was treated at 380°C for 1 hour. As a result, the film is completely vaporized.

Example 19

Add the oligomer of 10 grams of α-methylstyrene in the polyα-methylstyrene in 10 gram embodiment 18 (average molecular weight is that the α-methylstyrene oligomer of 450 is obtained by dichlorination (prepared by polymerizing α-methylstyrene in the presence of ethylaluminum) to form polyα-methylstyrene with a glass transition temperature of 65°C, and an emulsion was prepared in the same manner as in Example 16. When using this emulsion, a homogeneous film with a thickness of 12 micrometers was obtained. Next, the coating film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

Example 20

The same procedure as in Example 19 was followed except that 12 grams of poly-alpha-methylstyrene and 8 grams of dioctyl phthalate (glass transition temperature = 48°C) in Example 16 were used together so that the thickness It is a 25 micron clear film, but it has spot scattering and is somewhat uneven. Subsequently, the coating film was treated at 380° C. for 1 hour, and as a result, the film was completely vaporized.

Example 21

Dissolve 8 g of α-methylstyrene trimer and 12 g of poly-α-methylstyrene with a number average molecular weight of 120,000 in the presence of butyllithium in 20 ml of benzene , and then add the solution to an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 ml of water. Next, thoroughly mix with a homogenizer. Stirring under a reduced pressure of 100 mmHg, heating the solution at 40° C. to distill 18 ml of benzene, to the emulsion thus obtained was added an antifoaming agent (trade name SH5503, manufactured by Toray Dow Coaning Sili-con Co., Ltd), the weight of which was The ratio was 1/100000, and this emulsion was then coated on a glass plate and dried to form a uniform film with a thickness of 3 microns. Thereafter, the film was treated at 380°C for 1 hour, and as a result, the film was completely vaporized.

On the contrary, it was prepared by the same procedure as above, except that no defoaming agent was used, and in this case, shrinkage was observed on some parts of the glass surface, and the film was not uniform. However, when the film was treated at 380°C for 1 hour, the film was completely vaporized.

Example 22

Carry out by the same procedure of embodiment 21, difference is to use 20 grams of the oligomer that is obtained by polypropylene carbonate (number average molecular weight=80000) that polymerized propylene oxide and carbon dioxide are prepared by hydrolyzing with sodium hydroxide aqueous solution (molecular weight = about 4500) instead of poly-alpha-methylstyrene, and no trimer of alpha-methylstyrene was used. However, when an antifoaming agent is used, an intercalation copolymer of methylsiloxane and polyoxyalkylene (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KF351) is used again. In this case, a homogeneous film was formed without any similar residues being observed.

Example 23

Dissolve 8 g of trimer of α-methylstyrene and 12 g of poly-α-methylstyrene with a number average molecular weight of 120,000 by polymerizing α-methylstyrene in the presence of butyllithium in 20 ml of benzene Styrene, and this solution was added to an aqueous solution obtained by dissolving 1 g of sodium dodecylbenzenesulfonate in 100 ml of water. Next, thorough mixing was performed with a homogenizer, and the solution was heated at 40°C with stirring under a reduced pressure of 100 mmHg to distill 18 ml of benzene. The emulsion thus prepared was then coated on a glass plate and dried at 80°C to form a film with a thickness of 30 µm. Thereafter, the poly-α-methylstyrene film grown on glass was placed in a metallized apparatus at 10 ⁻⁵ mmHg to deposit 10 μm thick aluminum on the film soil. Furthermore, within 30 minutes, the glass was directly heated to 380°C while maintaining the reduced pressure, and as a result, a flat aluminum film was formed.

Comparative example 2

Aluminum was deposited without applying any emulsion, and as a result, an aluminum film without metallic luster was produced.

Example 24

The same procedure as in Example 23 was carried out, except that 20 grams of poly(propylene carbonate) (number average molecular weight = 80,000) obtained by hydrolyzing propylene oxide and carbon dioxide polymerization with aqueous sodium hydroxide solution was used to obtain the oligomer (molecular weight = about 4500) instead of poly-alpha-methylstyrene, and no trimer of alpha-methylstyrene was used. In this case, an aluminum film having a flat surface is similarly formed.

Claims (13)

1, a kind of preparation can divide the method for degrading film, and this method comprises that coating is dispersed in poly alpha methylstyrene or zinc-containing solid catalyst in the water and the water miscible liquid that makes, the step of this emulsion of drying then.

2, according to the method for claim 1, wherein water miscible liquid is to be dissolved in the solution that forms in the solvent by poly alpha methylstyrene or zinc-containing solid catalyst to be dispersed in the water, and evaporation then/remove is desolvated so that the content of solvent is that benchmark can be in 20 to 100%(weight with the weight of poly alpha methylstyrene or zinc-containing solid catalyst) make in the scope.

3, according to the process of claim 1 wherein that the concentration of poly alpha methylstyrene in the emulsion or zinc-containing solid catalyst is in 10 to 30%(weight) in the scope.

4, according to the process of claim 1 wherein that poly alpha methylstyrene or zinc-containing solid catalyst are dispersed in the water in the presence of tensio-active agent and defoamer.

5, according to the method for claim 4, wherein the amount of used defoamer is in 1/100000 to 1/1000 scope of emulsion weight.

6, according to the process of claim 1 wherein that poly alpha methylstyrene or zinc-containing solid catalyst are dispersed in the water in the presence of softening agent.

7, according to the process of claim 1 wherein that a poly alpha methylstyrene or zinc-containing solid catalyst are dispersed in the water, the aliphatic carboxylic acid esters, is as softening agent.

8, according to the process of claim 1 wherein that the number-average molecular weight of poly alpha methylstyrene is in 5000 to 1000000 scopes.

9, according to the process of claim 1 wherein that the second-order transition temperature of poly alpha methylstyrene is in 100 to 0 ℃ of scopes.

10, according to the process of claim 1 wherein water miscible liquid be by be softening agent and number-average molecular weight 50000 or lower and weight-average molecular weight/number-average molecular weight than be 3 or bigger poly alpha methylstyrene be dispersed in the water and make.

11, according to the process of claim 1 wherein that zinc-containing solid catalyst is that alkylene oxygen and carbon dioxide by a copolymerization 2-10 carbon atom makes.

12, according to the process of claim 1 wherein that the number-average molecular weight of zinc-containing solid catalyst is in 1000 to 1000000 scope.

13, a kind of preparation has the method for the metallic membrane of flat surface, and this method comprises and poly alpha methylstyrene or polyalkylene being dispersed in the water and the water miscible liquid that makes is coated on the uneven surface; Dry emulsion; Metal deposition is on poly alpha methylstyrene that forms or zinc-containing solid catalyst layer; The step of under the temperature of the heat decomposition temperature that is higher than poly alpha methylstyrene or zinc-containing solid catalyst, handling then.