JPH045685B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a process for making silicon-terminated oxypropylene polymers that can cure at room temperature to rubber-like materials upon exposure to atmospheric moisture. As two-component room temperature curing sealants and adhesives, thiol-based, urethane-based, etc. are already available on the market. In such two-component room temperature curing sealants, it is necessary to mix the main ingredient and the vulcanizing agent on-site immediately before use, but there are problems with the reproducibility of the mixing method, mixing time, etc. There is a problem that the performance during curing and after curing varies, and there is also the problem that once mixed, the entire product must be used immediately, otherwise it will be disposed of as waste. A one-component type was developed to solve these problems. As one-component types, thiocol type, urethane type and silicone type are provided on the market, but each of them has many problems. That is, the thiocol type has a fatal drawback in that the curing speed is very slow under normal conditions, so it can only be used in environments of high temperature and humidity. Urethane-based polymers are isocyanate-terminated polymers that harden at room temperature when exposed to atmospheric moisture;
Foaming occurs due to carbon dioxide gas generated during curing, inability to adhere to inert surfaces such as glass and ceramics without the aid of expensive primers such as silicone primer, and intermolecular interactions due to hydrogen bonding. It has many problems, such as insufficient elongation after curing because it has strong urethane and urea bonds in its molecules, and its high strength can cause the adherend to break. Silicon-based
It is a polysiloxane that undergoes hydrolysis and hardens when it comes into contact with moisture in the atmosphere, and has a hydrolyzable group such as acetoxy bonded to silicon at its end. This polymer cures rapidly in the presence of atmospheric moisture without harmful consequences such as foaming, and exhibits good adhesion without a primer to inert surfaces such as glass and ceramics. It is used for various purposes due to its characteristics. However, since it uses a special polymer called polysiloxane, it is very expensive, and it also has a problem that the adherend may be destroyed if it is brittle due to its high strength and low elongation after curing. A point is left. As mentioned above, these current 1
It must be said that the component type has various problems in terms of performance and price. Two methods have already been proposed as methods for inexpensively obtaining a silicon-based one-component type, which has almost been established in terms of performance. That is, the method proposed in Japanese Patent Publication No. 45-36319 and Japanese Patent Publication No. 46-12154 (hereinafter referred to as method A), and the method proposed in Japanese Patent Publication No. 46-30711 (hereinafter referred to as method B).
In both cases, the main chain of the polymer is an inexpensive organic polymer, a silicon-based functional group is introduced only at the terminal end, and this functional group is used to achieve curing. In Method B, a polyhydroxy compound such as a polyether polyol or a polyester polyol is used as a starting material, and at least 2 an isocyanate-terminated polymer having two urethane bonds, an organic group having a reactive hydrogen atom capable of reacting with the terminal isocyanate group on the isocyanate-terminated polymer and the silicon atom, and at least one on the silicon atom. This is a method for producing a one-component room temperature curable silicon-terminated polymer by reacting it with a special organosilicon compound such as γ-aminopropyltrimethoxysilane having two hydrolyzable groups. This silicon-terminated organic polymer has a hydrolyzable group on the terminal silicon atom that can undergo hydrolysis and condensation hardening when it comes into contact with moisture in the atmosphere, so it is as useful as conventional silicon-based polymers. It can be used as a component type sealant. Moreover, compared to silicon-based polymers, most of the polymers are considerably low-cost organic polymers such as polyester or polyether, and the high-priced silicon compound is present only at the ends of the organic polymer. The silicon-terminated organic polymer is considerably cheaper than conventional silicon-based one-component types. However, in the silicon-terminated organic polymer obtained by this method, the polyester polyol or the polyhydroxy compound such as the polyester polyol, and the organic polyisocyanate used as raw materials are quite expensive, and in addition, a silicon compound is added to the polymer terminal. Due to the fact that the special organosilicon compound used in the introduction, such as γ-aminopropyltrimethoxysilane, is very expensive, and because it requires many steps to be produced,
This results in a surprisingly expensive silicon-terminated organic polymer. In addition, the silicon-terminated organic polymer has at least 10 or more urethane bonds in one molecule of the polymer having a molecular weight of 10,000 or more because the molecular weight of the organic polymer portion is increased with organic polyisocyanate. Because the urethane bonds form crosslinks between molecules through hydrogen bonds, the polymer itself has a high viscosity and is very inconvenient to handle, and the cured product has high strength but low elongation. Therefore, this property has the problem that fragile adherends are destroyed. Furthermore, if even a small amount of isocyanate functional groups remain in the isocyanate-terminated polymer obtained during the manufacturing process, it will react with moisture in the atmosphere during the curing process, generate carbon dioxide gas, and cause foaming, impairing the properties of the cured product. Another problem is that the reaction must be completed strictly. Another proposed method, A, uses a polyhydroxy compound such as a polyether polyol or a polyester polyol as a starting material, and forms a polyester or polyester having an olefin group at the end by intervening an ester bond, carbonate bond, or urethane bond. By making an ether polymer and reacting the olefin group of the olefin-terminated polymer with a silicon hydride compound having at least one hydrolyzable group on a silicon atom and having a silicon hydrogen bond in the presence of a platinum catalyst. , a method for producing a one-component room temperature curable silicon-terminated polymer. In this method, intermediate olefin-terminated polymers obtained by intervening ester bonds and carbonate bonds are used, for example, in polyhydroxy compounds in the presence of pyridine, which are very expensive and require a lot of handling, such as allyl chloroformate. Because it is obtained by reacting special organic compounds that require special care, it is extremely expensive and impractical. Therefore, an olefin-terminated polymer obtained by interposing urethane bonds can be said to be the only practical intermediate raw material. A typical method for producing an olefin-terminated polymer obtained by interposing a urethane bond is to react a polyhydroxy compound with allyl isocyanate, or to react a polyhydroxy compound with a polyfunctional isocyanate compound such as toluene diisocyanate. to form an isocyanate-terminated polymer,
Thereafter, a method is used in which the terminal isocyanate group is reacted with a compound such as allyl alcohol. Therefore, the olefin-terminated polymer obtained by this production method has at least two urethane bonds per molecule, and these urethane bonds contain active hydrogen called nitrogen-hydrogen bonds. In Method A, a hydrosilicon compound is reacted with the olefin group of this olefin-terminated polymer to form a silicon-terminated organic polymer.This hydrosilicon compound not only reacts with the olefin bond but also forms a urethane bond. Since the hydrosilicon compound also reacts with active hydrogen present therein, there is a problem in that the hydrosilicon compound must be used in considerable excess relative to the olefin group in order to obtain the desired silicon-terminated organic polymer in a pure state. Furthermore,
When a halogenated silane compound such as methyldichlorosilane or trichlorosilane is used as the hydrosilicon compound, the halogenated silane compound may react with the urethane bond in the polymer and inhibit the hydrosilylation reaction. Therefore, it may be impossible to use these low-cost halogenated silane compounds. Therefore, it is necessary to use hydrosilicon compounds that do not contain halogen, such as methyldimethoxysilane or methyldiacetoxysilane, which are very expensive and do not have a very high reaction activity in the hydrosilylation reaction with respect to olefin groups. First, the resulting silicon-terminated organic polymer is also expensive. Furthermore, in Method A, a polyether polyol such as polypropylene glycol is mainly used as a starting material, but the polyether polyol can be produced by polymerization at 120°C or higher using a caustic alkali as a catalyst. In the method of producing at high temperature, the higher the molecular weight, the more likely the end of the polyether becomes an olefin end group such as an allyl group or an isopropenyl group due to chain transfer. To obtain ether, the molecular weight must be less than 3000. Therefore, in Method A, since these low molecular weight hydroxy group-terminated polyethers are used as raw materials, the silicon-terminated organic polymer itself obtained from this has a low molecular weight, and when used as a sealant, it will not harden. The problem is that the product has very low elongation properties, and its use as a sealant is extremely limited. Methods B and A, which were proposed as methods for manufacturing silicone-based one-component sealants at low cost, have been described above, but it can be seen that both methods still have many problems. As a result of various studies to solve these problems, the present inventors discovered that a specific and novel oxypropylene polymer having a hydrolyzable silicon functional group at the end met the purpose, and arrived at the present invention. did. The cured product obtained by exposing the polymer obtained according to the present invention to the atmosphere and curing it has a high molecular weight of the silicon-terminated oxypropylene polymer used, and furthermore, the polymer has a high molecular weight, and also has urethane bonds that form crosslinks between molecules. Because it does not have any functional groups, it improves the low elongation, which was a major problem with conventional one-component sealants, and has the characteristic of high elongation, which is especially useful for brittle adhesives. The silicon-terminated organic polymer of the present invention can be used in a very wide range of applications because it has the characteristic that it can be used without destroying the adherend. Furthermore, we have already proposed as an intermediate raw material for the silicon-terminated oxypropylene polymer used in the present invention a high molecular weight and inexpensive allyl-type olefin group-terminated polypropylene oxide (Japanese Patent Application Laid-open No. 13496/1983, Publication No. 50-149797) can be used.
In addition, this allyl-type olefin group-terminated polypropylene oxide does not have functional groups that adversely affect the reaction, such as urethane bonds, so it is a very inexpensive basic raw material as a hydrosilicon compound even in the hydrosilylation reaction stage, and is highly reactive. Since it has the advantage that halogenated silane compounds such as methyldichlorosilane or trichlorosilane can be easily used, the polymer obtained by the method of the present invention is characterized by being very inexpensive. That is, the present invention involves converting an oxypropylene polymer having a molecular weight of 6,500 to 15,000 and having an ether-type allyl olefin group at the terminal in the presence of a catalyst such as platinum into the general formula (wherein R is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1, or 2, and X is a group selected from a halogen, an alkoxy group, an acyloxy group, and a ketoximate group. (representing a group or atom) with a hydrosilicon compound represented by
at the end (In the formula, R, a, and X are the same as above) At least 1 group per molecule of the polymer
The object of the present invention is to provide a method for producing an oxypropylene polymer which can be cured into a solid elastic state upon contact with the atmosphere at room temperature. The oxypropylene polymer having an ether-type allylolefin group at the end, which is an inexpensive intermediate raw material used in the present invention, can be obtained by the method already proposed by us (Japanese Patent Application Laid-open No. 13496/1983, 50
-149797). To give one example, alkylene oxide is polymerized at a low temperature of 20°C to 100°C using caustic potash as a catalyst and an alcohol such as allyl alcohol, ethylene glycol, or trimethylolpropane as a cocatalyst. The molecular weight is increased by termination with an allyl halide compound such as allyl chloride or by treatment with a polyfunctional halide compound such as methylene chloride or bischloromethyl ether before terminating the polymerization with an allyl halide compound. By subsequently further treating with an allyl halogen compound, a high molecular weight oxyalkylene polymer having ether-type allyl olefin groups at almost all terminals can be obtained at once.
The alkylene oxide herein includes ethylene oxide, propylene oxide, 1-butene oxide, isobutylene oxide, etc., and the oxyalkylene polymer may be a homopolymer using these alkylene oxides alone or a mixture thereof. A copolymer may also be used. In the present invention, a propylene oxide homopolymer or a copolymer containing propylene oxide as one component is used. Regarding the molecular weight, any molecular weight between 500 and 15,000 can be used, but from the viewpoint of physical properties such as elongation, it is between 2,000 and 15,000.
15000 is valid. More preferably 4000
or more, particularly preferably 5000 or more. In the present invention, those having a number of 6,500 to 15,000 are used. When the molecular weight exceeds 15,000, the viscosity of the silicon-terminated oxypropylene polymer increases, making it difficult to handle when used as a curable composition. In addition, the special public service
Publication No. 17553 and Special Publication No. 45-36319
Silicon-terminated polyethers with molecular weights from 300 to 12,000 are described. However, as mentioned above, it is extremely difficult to obtain a high molecular weight polypropylene glycol as a raw material, so these publications also state that the preferred range is 1000 to 2000. Therefore, although these publications describe polymers having a molecular weight of 300 to 12,000, there is no substantial description of the large molecular weight range of 6,500 to 15,000 as used in the present invention. 6500〜
An oxypropylene polymer having a molecular weight of 15,000 can be easily produced by adjusting the type and amount of alcohol used as a cocatalyst, adjusting the polymerization temperature, or adjusting the type and amount of a polyfunctional halogen compound. can be obtained. The oxypropylene polymer obtained in this way has an ether-type allylolefin group at the end, and is clearly different from the oxyalkylene polymer that has a functional group such as a urethane bond in the polymer molecule used in Method A. They are different. The silicon-terminated oxypropylene polymer of the present invention is
The olefin group of an oxypropylene polymer having an ether-type allylolefin group at the end is reacted with a hydrosilicon compound in the presence of a group transition metal catalyst, and an organic silyl group is introduced at the end of the oxypropylene polymer. The hydrosilicon compound used herein has the following general formula. This general formula (In the formula, R, X and a are as described above.) Specific examples of the hydrosilicone compounds contained in Halogenated silanes; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane and bis(methylethylketoximate)methylsilane; triacetoxysilane, methyldiacetoxysilane and Acyloxysilanes such as phenyldiacetoxysilane; ketoximate silanes such as tris(acetoximate)silane, bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane. The ether-type allyl olefin group-terminated oxypropylene polymer described above is A
Since there are no functional groups with active hydrogen bonds such as urethane bonds in the molecule as proposed in the method, side reactions occur with the active hydrogen groups in these molecules and the hydrosilicon compound is consumed. Instead, it reacts very efficiently with the olefin group present at the end of the oxypropylene polymer to form a silicon-terminated oxypropylene polymer. Therefore, if a stoichiometric amount of the hydrosilicon compound is used with respect to the terminal olefin group, silicon terminals can be sufficiently obtained. Furthermore, the use of an ether-type allylolefin group-terminated oxypropylene polymer is a very inexpensive basic raw material for a hydrosilicon compound, and another major feature is that highly reactive halogenated silanes can be easily used. . In method A, functional groups such as urethane bonds present in the molecule and halogenated silanes form complex salts or react with each other, adversely affecting the hydrosilylation reaction, and causing oxypropylene polymer It is no exaggeration to say that these halogenated silanes are practically unusable because they cause secondary polymer decomposition. Since the ether-type allyl olefin-terminated oxypropylene polymer does not have a functional group such as a urethane bond in the molecule, the use of these halogenated silanes will not have a negative effect on the hydrosilylation reaction, and will react to form oxypropylene. It does not cause secondary polymer decomposition of the polymer. Silicon-terminated oxypropylene polymers obtained using halogenated silanes cure rapidly at room temperature while emitting hydrogen chloride when exposed to air, but there are problems with the irritating odor and corrosion caused by hydrogen chloride, so there is limited use. It is desirable to subsequently convert the halogen functional group to another hydrolyzable functional group, since it can only be used practically in certain applications. Hydrolyzable functional groups include alkoxy groups, acyloxy groups, aminoxy groups, amide groups,
Included are acid amide groups and ketoximate groups. There are various methods for converting halogen functional groups into these hydrolyzable functional groups. for example,
Methods for converting to alkoxy groups include methanol, ethanol, 2-methoxyethanol, sec
- alcohols and phenols such as butanol, ter-butanol and phenol; sodium, potassium and lithium salts of alcohols and phenols; alkyl orthoformates such as methyl orthoformate and ethyl orthoformate; etc. A specific example is a method of reacting with a halogen functional group. Methods for converting into acyloxy groups include a method of reacting carboxylic acids such as acetic acid and propionic acid; acid anhydrides such as acetic anhydride; sodium salts, potassium salts, and lithium salts of carboxylic acids; etc. with a halogen functional group. Specific examples are listed. As a method for converting into an aminoxy group, N,
Hydroxylamines such as N-dimethylhydroxylamine, N,N-methylphenylhydroxylamine and N-hydroxylpyrrolidine;
Specific examples include a method in which sodium salt, potassium salt, lithium salt, etc. of hydroxylamines are reacted with a halogen functional group. As a method for converting into an amide group, N,N-
dimethylamine, N,N-diethylamine, N,
Specific examples include methods of reacting primary and secondary amines such as N-methylphenylamine and pyrrolidine; sodium salts, potassium salts, and lithium salts of primary and secondary amines; etc. with halogen functional groups. It will be done. As a method for converting into an acid amide group, acid amides such as acetamide, formamide and propionamide having at least one hydrogen atom on a nitrogen atom; sodium salts, potassium salts and lithium salts of the acid amides; etc. A specific example is a method of reacting with a halogen functional group. Regarding the silicon functional group introduced at the end of the oxypropylene polymer by the hydrosilylation reaction, it is not only converted into other hydrolyzable functional groups in the case of halogen functional groups, but also in the case of other alkoxy groups and acyloxy groups. , if necessary, can be converted into a hydrolyzable functional group such as an aminoxy group. The reaction temperature for converting the hydrolyzable functional groups on the terminal silicon directly introduced by the hydroxylation reaction into other hydrolyzable functional groups is 20°C to 120°C.
°C is appropriate. These conversion reactions can also be accomplished with or without the use of solvents, but if used, inert solvents such as ethers and hydrocarbons are suitable. The production of the above silicon-terminated oxypropylene polymer can be illustrated as follows. (In the formula, Y is an alkoxy group, an acyloxy group,
In the present invention, a hydrosilicon compound is reacted with the terminal olefin group of the oxypropylene polymer (X, R, and a are as described above). The step requires a transition metal complex catalyst.
As transition metal complex catalysts, group transition metal complex compounds selected from platinum, rhodium, cobalt, palladium, and nickel are used as already reported in Journal of the Society of Organic Synthetic Chemistry, vol. 28, p. 919 (1970). Used effectively. In particular, platinum-based catalysts such as chloroplatinic acid, platinum metal, platinized activated carbon, platinum chloride, and platinum olefin complexes are excellent. This hydrosilylation reaction can be achieved at any temperature from 30°C to 150°C, but it is preferably carried out at a temperature from 60°C to 120°C in order to suppress side reactions. The reaction time is satisfactorily achieved within 2 hours. A solvent may or may not be used, but when used, inert solvents such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons are suitable. The oxypropylene polymer to be subjected to the hydrosilylation reaction preferably has ether-type allyl olefin groups at all ends, but depending on the raw material, a small amount of hydroxyl groups (-OH) may remain as end groups. There's something I'm doing. In such cases, when halogenated silanes are used in the hydrosilylation reaction, the hydroxy group and the halogen of the halogenated silanes react to generate hydrogen halide, and the hydrogen halide converts oxypropylene into hydrogen. Undesirable side reactions may occur in which the combined molecules are cleaved. In addition, at this time, the polymer becomes a polymer having an organosilicon terminal group connected to a silicon atom through an alkoxy bond, and the organosilicon terminal group is

[Formula] Since it is a hydrosilicon group with a bond, moisture in the atmosphere is absorbed during the curing stage when exposed to the atmosphere.

[Formula] Reacts with the bond and generates hydrogen gas, which may cause the inconvenience of foaming the cured product. Therefore, prior to the hydrosilylation reaction using hydrosilicon compounds,

[Formula] Pre-treatment with a halogenated silane that does not have a bond, so that no hydroxy group (-OH) remains at the polymer end, and after removing unreacted halogenated silanes and generated hydrogen halide, hydrosilylation reaction takes place. It is preferable to take the following steps: used for pre-processing

[Formula] Specific examples of the halogenated silanes having no bond include tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and the like. However, the hydrosilicon compounds used in the hydrosilylation reaction are alkoxysilanes,
In the case of acyloxysilanes and acyloxysilanes, no pretreatment is necessary since no undesirable reaction with the hydroxyl group (-OH) at the end of the polymer occurs. In the case of halogenated silanes, if almost all of the polymer terminal groups are allylic olefin groups, pretreatment is not necessary at all, so pretreatment is not necessarily required prior to the hydrosilylation reaction. You can use it as you like depending on the purpose. As for the pretreatment conditions, it is sufficient to carry out the treatment at room temperature for 1 minute to 30 minutes, and it is better to remove unreacted halogenated silanes and generated hydrogen halide prior to the hydrosilylation reaction. The curing mechanism in which the silicon-terminated polyoxypropylene polymer of the present invention is exposed to the atmosphere, forms a three-dimensional network structure, and hardens into a solid having rubber-like elasticity is that the hydrolyzable group (X) is is substituted with a hydroxyl group, and then the ≡Si-OH groups are condensed to form a siloxane bond (≡Si-O-Si≡) and cured, or the ≡Si-OH group and the Si-X group are The reaction produces siloxane bonds and HX, resulting in curing. Therefore, since the curing rate varies depending on atmospheric temperature, relative humidity, and the type of hydrolyzable group, it is necessary to take into consideration the type of hydrolyzable group when using the composition. It goes without saying that the silicon-terminated oxypropylene polymer of the present invention must be stored under anhydrous conditions so that it does not come into contact with water until it is actually used. In curing the composition using the silicon-terminated oxypropylene polymer of the present invention, a curing accelerator may or may not be used. If curing accelerators are used, metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, tin octylate and dibutyltin dilaurate; dibutylamine-2-ethylhexoate, etc. Amine salts; and other acidic and basic catalysts are useful. The amount of these curing accelerators is approximately 0.001 of the composition.
It is preferable to use the curing accelerator in an amount of ~10% by weight, and these curing accelerators can be added at any stage during or after the production of the polymer. Compositions employing the silicon-terminated oxypropylene polymers of this invention may be modified by incorporating various fillers. Fillers include reinforcing fillers such as fused silica, precipitated silica and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, powdered quartz, titania, ferric oxide, zinc oxide and talc, etc. Non-reinforcing fillers; fibrous fillers such as asbestos, glass fibers and filaments may be used. It is desirable that these fillers be dried before being mixed with the polymer. In addition to these fillers, compositions using the polymers of the present invention can be further modified by adding additives such as plasticizers, pigments, ultraviolet absorbers, antioxidants, flame retardants, and insulating agents. Metamorphosis is possible. Of course, it is desirable to use these additives after thoroughly drying them. Compositions using the silicon-terminated polymers of the present invention are useful as coating compositions and sealing compositions for buildings, aircraft, automobiles, etc. Additionally, it can be used alone or with the aid of a primer to adhere to a wide range of substrates such as glass, porcelain, wood, metals, polymeric materials, etc., and is therefore used in various types of sealing and adhesive compositions. It is possible. Furthermore, it is useful as a food packaging material, a casting rubber material, and a molding material. Hereinafter, examples will be specifically described. Comparative Example 1 400 parts of an oxypropylene polymer having a molecular weight of about 4000 and having 96% allyl-type olefin groups at its terminals is placed in a pressure-resistant glass reaction vessel for electromagnetic stirring type 1 which is purged with nitrogen. This oxypropylene polymer is purified by dehydration and does not contain water or metal salts. followed by methyldimethoxysilane under a nitrogen stream.
Add 23.4 parts and 0.006 parts of platinum/ethylene complex,
React at 100°C for 1 hour with stirring. After the reaction is complete,
Unreacted methyldimethoxysilane was removed under reduced pressure to obtain a polymer with a molecular weight of 4,200. 120 parts of calcium carbonate, 40 parts of fused silica, 40 parts of dioctyl phthalate, 2 parts of antioxidant and 2 parts of dibutyltin laurate are added to this system and mixed uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick within 2 hours. 10 days later,
A sheet with a thickness of 1.0 mm is obtained, and the properties of the sheet are as follows: Shore A hardness: 32.3, tensile strength:
The weight was 5.4Kg/cm ² and the elongation at break was 360%. Comparative Example 2 Comparative Example 1 except that 25.3 parts of methyldichlorosilane was used instead of methyldimethoxysilane and 0.08 parts of 5% Pt/c was used instead of the platinum-ethylene complex.
The hydrosilyl reaction is carried out under the same reaction conditions. After the reaction is complete, unreacted methyldichlorosilane is removed under reduced pressure. Add 120 parts of calcium carbonate and 2 parts of antioxidant to the system and mix uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick within 2 minutes. 1 day later, 2.0
A sheet with a thickness of mm is obtained, and the properties of the sheet are as follows: shore A hardness 26, tensile strength 3.2
Kg/cm ² and elongation at break was 180%. Comparative Example 3 Comparative Example 1 except that 35.7 parts of methyldiacetoxysilane was used instead of methyldimethoxysilane.
The hydrosilyl reaction is carried out under the same reaction conditions. After the reaction is completed, unreacted methyldiacetoxysilane is removed under reduced pressure. Dioctyl phthalate 40 in this system
120 parts of calcium carbonate and 2 parts of antioxidant are added and mixed uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick within 5 minutes. After 4 days, a sheet having a thickness of 1.3 mm was obtained, and the properties of the sheet were Shore A hardness of 28, tensile strength of 5.6 Kg/cm ² and elongation at break of 320%. Example 1 90 mol of allylic olefin group with a molecular weight of approximately 6500
Purified oxypropylene polymer terminated in %
Transfer 500 parts to a pressure-resistant glass reaction vessel for 1.5 liters with electromagnetic stirring and purged with nitrogen. Add 5 parts of methyldichlorosilane under a nitrogen stream, stir the reaction at room temperature for 5 minutes, and then
Unreacted methyldichlorosilane and slightly formed hydrogen chloride are removed under reduced pressure. The reaction vessel was replaced with nitrogen, and methyldichlorosilane was added under a nitrogen stream.
Add 19.5 parts and 0.04 parts of 5% Pt/c, and react at 90°C for 1 hour with stirring. After the reaction is complete, unreacted methyldichlorosilane is removed under reduced pressure. The reaction vessel was purged with nitrogen, 16.6 parts of finely ground sodium methoxide was added, and the mixture was stirred at 80° C. for 1 hour to react with the Cl ₂ Si (CH ₃ ) group at the end of the polymer. After cooling to room temperature, a polymer with a molecular weight of 6700 was obtained. 150 parts of calcium carbonate, 50 parts of fused silica, 50 parts of dioctyl phthalate, 2 parts of antioxidant and 2 parts of dibutyltin laurate are added to this system and mixed uniformly under a nitrogen stream. The mixture was thoroughly kneaded with three rolls for paint under a nitrogen stream, and then poured onto a tin plate and exposed to the atmosphere, whereupon it became non-tacky within one hour. 14
After days, a sheet with a thickness of 2.0 mm is obtained,
The properties of the sheet were Shore A hardness of 34, tensile strength of 6.8 Kg/cm ² , and elongation at break of 420%. Example 2 Pretreatment and hydrosilylation reactions were carried out using the same procedures and quantities as in Example 1, and the terminal Cl ₂ Si
A polymer having (CH ₃ )- groups was obtained. Under a nitrogen stream, 30.2 parts of finely ground 2-(methoxy)ethoxysodium is added and reacted with the Cl ₂ Si (CH ₃ )- group at the end of the polymer while stirring at 80° C. for 1 hour. After cooling to room temperature, 150 parts of calcium carbonate, 50 parts of fused silica,
Add 50 parts of dioctyl phthalate and 2 parts of antioxidant and mix uniformly under a nitrogen stream. The mixture was thoroughly kneaded with three rolls for paint under a nitrogen stream, and then poured onto a tin plate and exposed to the atmosphere, whereupon it became non-tacky within 6 hours. After 21 days, a sheet having a thickness of 1.6 mm was obtained, and the properties of the sheet were: Shore A hardness of 26, tensile strength of 4.2 Kg/cm ² and elongation at break of 400%. Example 3 Pretreatment and hydrosilylation reactions were carried out using the same procedures and quantities as in Example 1, and the terminal Cl ₂ Si
A polymer having (CH ₃ )- groups was obtained. Add 31.4 parts of acetic anhydride under a nitrogen stream and react at 50°C for 1 hour.
A polymer having a (CH ₃ COO) ₂ Si(CH ₃ )- group at the end. The system is stripped of volatiles under reduced pressure. After cooling to room temperature, 150 parts of calcium carbonate, 50 parts of fused silica and 2 parts of antioxidant are added and mixed uniformly under a nitrogen stream. The mixture became non-stick within 15 minutes when poured onto a tin plate and exposed to the atmosphere. After 2 days, a sheet with a thickness of 2.4 mm is obtained, the properties of which are Shore A hardness 34,
The tensile strength was 3.8 Kg/cm ² and the elongation at break was 340%. Comparative Example 4 Pretreatment and hydrosilylation reaction were carried out using the same procedures and amounts as in Comparative Example 1 to obtain a polymer having terminal ( _CH3O ) _2Si ( _CH3 )- groups. By adding 35.7 parts of diethylhydroxylamine under a nitrogen stream and heating the system to remove the generated methanol, a polymer having (C ₂ H ₅ )N-O) ₂ Si(CH ₃ )- group was obtained. Obtained. 120 parts of calcium carbonate, 40 parts of fused silica, 40 parts of dioctyl phthalate and 2 parts of an antioxidant are added to the polymer under a nitrogen stream and mixed uniformly. The mixture became non-stick within 1 hour when poured onto a tin plate and exposed to the atmosphere. After 14 days, a sheet with a thickness of 1.8 mm is obtained, and the properties of the sheet are as follows: Shore A hardness
34, tensile strength was 5.2 Kg/cm ² , and elongation at break was 310%. Comparative Example 5 Methyldimethoxysilane was replaced with methyldimethoxysilane.
Other than using (dimethylketoxime)silane,
Hydrosilyl reaction is carried out under the same reaction conditions as in Comparative Example 1. After the reaction is completed, unreacted methyldi-(dimethylketoxime)silane is removed. Add 40 parts of dioctyl phthalate, 120 parts of calcium carbonate, and 2 parts of an antioxidant to the system and mix uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick within 5 minutes. Example 4 20.6% of sodium dimethylamide [NaN(CH ₃ ) ₂ ] instead of 2-(methoxy)ethoxysodium
The reaction was carried out in the same manner as in Example 2, except that 100% of the reaction mixture was used, to obtain a polymer having [((CH ₃ ) ₂ N) ₂ Si(CH ₃ )-] groups at the terminals. Add 10 parts of dioctyl phthalate, 120 parts of calcium carbonate and 2 parts of an antioxidant to the system and mix uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick after 24 hours. Example 5 Sodium (N-methyl)acetamide [CH ₃ CO
-N(CH ₃ )Na] was reacted in the same manner as in Example 2 except that 27.4 parts of [(CH ₃ CO-
A polymer having N(CH ₃ )) ₂ Si(CH ₃ )-] groups was obtained. Add 40 parts of dioctyl phthalate, 120 parts of calcium carbonate, and 2 parts of an antioxidant to the system and mix uniformly under a nitrogen stream. The mixture was poured onto a tin plate and exposed to the atmosphere and became non-stick after 24 hours. Example 6 2.64 parts of _{methyldimethoxysilane} and 0.01 part of a 10% isopropanol solution of _H2PtCl6.6H2O were added to 100 parts of an oxypropylene polymer having an allyl ether group with a molecular weight of about ₈₀₂₀ , and the mixture was heated to 80% under a nitrogen atmosphere.
The reaction was carried out at .degree. C. for 4 hours to obtain a polymer having a molecular weight of 8,200 and having a methyldimethoxysilyl group at the end. The following compound was made using the obtained polymer, and after kneading it well by passing it through three paint rolls three times, a type 2 H type sample specified in JIS A-5758 was prepared. After curing according to the standard curing specified by JIS,
A tensile test was conducted. The results are shown in Table 1. Silyl ether group-terminated oxypropylene polymer
100 parts by weight plasticizer (dioctyl phthalate 60 〃 Calcium carbonate 120 〃 Titanium oxide 30 〃 Dibutyltin dilaurate 2 〃 Example 7 1.66 parts of methyldimethoxysilane and H ₂ Add 0.01 part of a 10% isopropanol solution of PtCl ₆ 6H ₂ O and mix under nitrogen atmosphere.
The reaction was carried out at 80° C. for 4 hours to obtain a polymer having a molecular weight of 13,000 and having a methyldimethoxysilyl group at the end. The resulting polymer was used to make formulations similar to those shown in Example 6, and tensile tests were conducted in the same manner. The results are shown in Table 1. Comparative Example 6 Using the polymer obtained in Comparative Example 1, Example 6
A formulation similar to that shown in was made and tensile tested in a similar manner. The results are shown in Table 1. Example 8 Using the polymer obtained in Example 1, Example 6
A formulation similar to that shown in was made and tensile tested in a similar manner. The results are shown in Table 1. Comparative Example 7 7.6 parts of _{methyldimethoxysilane} and 0.01 part of a 10% isopropanol solution of _H2PtCl6.6H2O were added to 100 parts of an oxypropylene polymer having an allyl ether group with a molecular weight of about ₂₈₀₀ , and the mixture was heated to 80% under a nitrogen atmosphere.
The reaction was carried out at ℃ for 4 hours to obtain a polymer having a molecular weight of 3,000 and having a methyldimethoxysilyl group at the end. The resulting polymer was used to make formulations similar to those shown in Example 6, and tensile tests were conducted in the same manner. The results are shown in Table 1.

[Table] As is clear from Table 1, it is clearly seen that when the molecular weight is 6500 or more, the modulus is low and the elongation is significantly increased. A similar experiment was attempted using a polymer with a molecular weight of 18,000, but the viscosity was too high and it could not be prepared into a sealant composition.

Claims (1)

[Scope of Claims] 1. An oxypropylene polymer having a molecular weight of 6,500 to 15,000 and having an ether-type allyl olefin group at the end is prepared by adding an oxypropylene polymer having a molecular weight of 6,500 to 15,000 in the presence of a group transition metal, (wherein R is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1, or 2, and X is a group selected from a halogen, an alkoxy group, an acyloxy group, and a ketoximate group. (representing a hydrolyzable group) with a hydrosilicon compound represented by
Optionally, the silicon-terminated polymer obtained by further converting the hydrolyzable group A method for manufacturing a sealant characterized by incorporating a filler.