AU650872B2 - Oxypropylene polymer containing reactive silicon group and production thereof - Google Patents
Oxypropylene polymer containing reactive silicon group and production thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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Description
PCT
OPI DATE 30/10/91 AQJP DATE 05/12/91 APPLN. ID 75756 91 PCT NUMBER PMR/J91/00461 (51) 1W N5iX (11) [AAU V: WO 91/15536 C08G 65/32 Al (43)MM IJ f] 1] 1991* 1 OM179 (17, 10. 1991) (22) [NF bI l1991A*4J98[(08. 04. 91) %ttr, *W 2/9 45 43 I990&4.9EC 09. 04. 90) j (KANEGAFUCHI CHEMICAL INDUSTRY CO..LTD.) C JP/J P) 7F530 Osaka, (JP) (72) Y'L MEBR*(FUJITA. Masayuki )CJP/JP) *MFH11(HOMMA, Mic h ih id e CJP/J P 7676 A*A&-A1 AT2j63-9 Hyogo, (JP) 39# 2(WAKABAYASHI. Hiroshi )CJP/JP) 5 2 J8 1 02 Hy og o, (J P) (74) {t9A IfP± XMX-- !n(TSUTADA, Ak iko e t alI.) 7-541 ~IjL.8I~Osaka, (JP) AU, CA, JPF, US.
(54) Title :OXYPROPYLENE POLYMER CONTAINING REACTIVE SILICON GROUP AND PRODUCTION THERE-
OF
C H CEH- C H 2 -0 (57) Abstract A novel oxypropylene polymer containing a reactive silicon group, wherein the main polymer chain essentially comprises the repeating units of formula at least one reactive silicon group and at least one urethane bond are present at the terminals of the polymer chain, the ratio of Mw to Mn is 1.5 or less, and the number-average molecular weight is 3,000 or above. The production process comprises reacting an oxypropylene polymer having a ratio or Mw to Mn of 1.5 or less and a number-average molecular weight per unit terminal function or 1,500 or above with a compound having both a reactive silicon group and an isocyanate group.
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DESCRIPTION
REACTIVE SILICON GROUP-CONTAINING OXYPROPYLENE POLYMER AND METHOD OF PRODUCING SAME TECHNICAL FIELD This invention relates to a novel oxypropylene polymer which contains a reactive silicon group and to a method of producing the same.
BACKGROUND ART So far, various room temperature curing polymers have been developed which can be cured to rubber-like substances by the action of moisture. Thus, oxypropylene polymers containing a reactive silicon group (a group which is a silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and can form a siloxane bond) are also known.
However, since it is difficult to produce high molecular weight polyoxypropylene with a narrow molecualr weight distribution (great monodispersity), the known reactive silicon group-containing polyoxypropylene species are only those showing a broad molecular weight distribution (great polydispersity).
Recently, it has been reported that polyoxypropylene with a narrow molecualr weight distribution can be __i 2 obtained. The present inventors found that polymers derived from polyoxypropylene having a narrow molecualr weight distribution, whi h is used as the main chain, by introducing a reactive silicon group and a urethane bond terminally to said main chain have a low viscosity, hence are easy to handle, before curing and, after curing, give cured products having excellent tensile characteristics as well as good chemical i resistance and water resistance. This finding has now led to the present invention.
DISCLOSURE OF INVENTION The reactive silicon group-containing oxypropylene polymer of this invention is an oxypropylene polymer the main polymer chain of which is essentially composed of a repeating unit of the formula C H -CH-CH 2 0and which has at least one terminal reactive silicon group and at least one terminal urethane bond. It has an Mw/Mn ratio of not more than 1.5 and a number average molecular weight of not less than 3,000.
The production method of this invention is characterized by reacting an oxypropylene polymer having an 3- Mw/Mn ratio of not more than 1.5 and a number average molecular weight per terminal functional group of not less than 1,500 with a compound having a reactive silicon group and an isocyanato group.
BEST MODE FOR CARRYING OUT THE INVENTION The "reactive silicon group" as so termed herein is-not limited to any particular species but may typically includes groups of the general formula (1) shown below: 2-b 3-a Si -O Si X (1 X b In the above formula, R 1 and R 2 each is an alkyl group containing 1 to 20 carbon atoms, an aryl group Scontaining 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group of the formula 3 SiO-. Where there are two or 1 2 more R or R groups, they may be the same or different. R' is a monovalent hydrocarbon group containing 1 to 20 carbon atoms. The three R' groups may be the same or different. X is a hydroxyl group or a hydrolyzable group and, where there are two or more X groups, they may be the same or different, a is 0, 1, t 7 4- 2 or 3 and b is 0, 1 or 2. The number b may vary in the m groups of the formula Ri S2-b -S i-O- Sb m is an integer of 0 or 1 to 19. The following condition shall be satisfied: a Ib 1.
The hydrolyzable group represented by the above-mentioned X is not particularly limited but may be any hydrolyzable group known in the art. More specifically, there may be mentioned a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximato group, an amino group, an amido group, an acid amido group, an aminoxy group, a mercapto group, an alkenyloxy group and the like. Among these, the hydrogen atom and alkoxy, acyloxy, ketoximato, amino, amido, aminoxy, mercapto and alkenyloxy groups are preferred. From the viewpoint of mild hydrolyzability and easy handling, alkoxy groups are particularly preferred.
One to three such hydrolyzable groups or hydroxyl groups may be bound to one silicon atom, and (a Zb) is preferably equal to 1 to 5. Where there are two or more hydrolyzable groups or hydroxyl groups in the reactive silicon group, they may be the same or different.
The reactive silicon group may contain one silicon atom or two or more silicon atoms. In the case of a reactive silicon group comprising silicon atoms linked to one another via a siloxane bonding or the like, said group may contain about 20 silicon atoms.
Reactive silicon groups of the following general formula are preferred because of ready availability.
R
2 3-a I (2) Si -X i 2 X 2 In the above formula, R X and a are as defined above.
1 2 Specific examples of R and R appearing in the general formula given hereinabove include, among others, alkyl groups, such as methyl and ethyl, cycloalkyl groups, such as cyclohexyl, aryl groups, such as phenyl, aralkyl groups, such as benzyl, and triorganosiloxy groups of the formula 3 SiO- in which R' is methyl or phenyl. Among these, methyl is particularly preferred.
L i ilC i CIDT-rrr L PlaCI~-CIIIIII---- 6 The oxypropylene polymer should recommendably contain at least one, preferably 1.1 to 5 reactive silicon groups per molecule thereof. When the number of reactive silicon groups contained in the polymer on the per-molecule basis is less than 1, the curability becomes inadequate and a good rubber elastic behavior can hardly be developed.
The oxypropylene polymer contains at least one reactive silicon group terminally to the molecular chain thereof. It may contain a reactive silicon group internally to said chain. When the reactive silicon group occurs terminally to the molecular chain, as in the present invention, the oxypropylene polymer component contained in the finally formed cured products can have an increased number of effective network chains and therefore a rubber-like cured product showing high strength and high elongation (low elasticity) can readily be obtained.
The "urethane bond" so termed herein means a bond represented by -NHCOO-.
The oxypropylene polymer, which constitutes the main polymer chain in the polymer of this invention is essentially composed of a repeating unit of the formula c H 3
-CH-CH
2 -0- 7 This oxypropylene polymer may be straight-chained or branched, or a mixture of these. It may further contain a small proportion of another monomer unit or the like.
The oxypropylene polymer that can effectively be used has a number average molecular weight of not less than 3,000. The number average molecular weight of said polymer should preferably be not less than 3,000 when the polymer is straight-chained, and not less than 5,000 when the polymer is branched. More preferably, the polymer should have a number average molecular weight of 6,000 to 30,000. Furthermore, in this oxypropylene polymer, the weight average molecular weight/number average molecular weight ratio (Mw/Mn) is not more than 1.5, hence the molecular weight distribution is very narrow (the monodispersity is great). The value of Mw/Mn should preferably be not more than 1.4, more preferably not more than 1.3. The molecular weight distribution can be measured by various methods.
Generally, however, the measurement method most commonly used is gel permeatson chromatography (GPC). Since the molecular weight distribution is narrow in that manner despite the great number average molecular weight, the polymer of the invention has a low viscosity before curing, hence is easy to handle and, after curing, I F 8 shows a good rubber elastic behavior.
The polymer of this invention has a terminal urethane bond, so that the cured products after curing are excellent in strength and elongation.
For producing the reactive silicon group-containing oxypropylene polymer of the invention, it is only necessary to react an oxypropylene polymer having a terminal functional group (hereinafter referred'to as functional group such as a hydroxyl group, with a compound having a reactive silicon group and an isocyanato group reactive with said functional group Y.
The functional group Y-containing oxypropylene polymer to be used should be an oxypropylene polymer having an Mw/Mn ratio of not more than 1.5 and a number average molecular weight per terminal functional group of not less than 1,500.
The isocyanato group- and reactive silicon group-containing compound includes, but is not limited to, such typical examples as y-isocyanatopropyltriethoxysilane, y-isocyanatopropylmethyldimethoxysilane, y-isocyanatopropyltrimethoxysilane and the like isocyanato-containing silanes.
The production method of the invention which comprises reacting an oxypropylene polymer having a terminal functional group Y with a compound having an
^UP
f CF 9 isocyanato group and a reactive silicon group, as mentioned above, allows introduction of the reactive silicon group in one step without taking the complicated prior art reaction steps.
The reactive silicon group-containing oxypropylene polymer of the invention, when exposed to air, forms a three-dimensional network under the action of moisture hardens to a solid having rubber-like elasticity.
In curing the polymer of this invention, a silanol condensing catalyst (curing catalyst) may be used or may not be used. When a silanol condensing catalyst is used, it may be selected from a wide variety of known ones. As typical examples thereof, there may be mentioned such silanol condensing catalysts as titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octanoate and tin naphthenate; reaction products from dibutyltin oxide and phthalate esters; dibutyltin diacetylacetonate; organic aluminum compounds, such as aluminum trisacetyl-acetonate, aluminum tris(ethyl acetoacetate) and diisopropoxyaluminum ethyl aceto- I acetate; chelate compounds such as zirconium tetracetylacetonate and titanium tetracetylacetonate; lead octanoate; amine compounds, such as butylamine, octyl- I i i i -L 1~3~ 10 amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylnorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo- [5.4.0]undecene-7 (DBU), and salts of such amine compounds with carboxylic acids and so forth; low molecular weight polyamide resins obtained from an excess of a polyamine and a polybasic acid; reaction products from an excess of a polyamine and an epoxy compound; amino-containing silane coupling agents, such as y-aminopropyltrimethoxysilane and -aminoethyl)aminopropylmethyldimethoxysilane; and other known silanol condensing catalysJ, such as ac-1. catalysts and basic catalysts. These catalysts may be used either singly or in combination in the form of a mixture of two or more of them.
These silanol condensing catalysts are used preferably in an amount of about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the oxypropylene polymer.
When the amount of the silanol condensing catalyst is too small as compared with the oxypropylene polymer, 11 the rate of curing may be slow in certain instances and the curing reaction can hardly proceed to a satisfactory extent in some instances. On the other hand, if the amount of the silanol condensing catalyst is too large relative to the oxypropylene polymer, local heat generation and/or foaming may occur during curing, unfavorably making it difficult to obtain good cured products.
The reactive silicon group-containing oxypropylene polymer of the invention may be modified by incorporating thereinto various fillers. Usable as the fillers are reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, active zinc white, and "shirasu" balloons; and fibrous fillers such as asbestos, glass fibers and filaments.
For obtaining cured compositions affording high Sstrength using such fillers, a filler selected from among fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated finely divided calcium carbonate, calcined clay, clay, active zinc white and the like is mmr^ ~l 12 used in the main in an amount within the range of 1 to 100 parts by weight per 100 parts by weight of the reactive silicon group-containing oxypropylene polymer to give favorable results. For obtaining cured compositions affording low strength and high elongation, a filler selected from among titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide,"shirasu"balloons and the like is used in the main in an amount within the range of 5 to 200 parts by weight per 100 parts by weight of the reactive silicon group-containing oxypropylene polymer to give favorable results. Of course, these fillers may be used either alone or in combination as a mixture of two or more of them.
In using the reactive silicon group-containing oxypropylene polymer in accordance with the invention, a plasticizer may be used more effectively in combination with the filler since the use thereof may provide the cured products with an increased elongation and/or allow incorporation of fillers in large amounts. This plasticizer is any one in common and general use.
Thus, for instance, phthalate esters, such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phathalate; aliphatic dibasic acid esters, such as dioctyl adipate, isodecyl succinate and dibutyl sebacate;
V
13 glycol esters, such as diethylene glycol dibenzoate and pentaerythritol esters; aliphatic esters, such as butyl oleate and methyl acetylricinoleate; phosphate esters, such as tricresyl phosphate, trioctyl phosphate and octyl diphenyl phosphate; epoxy plasticizers, such as epoxidized soybean oil, and benzyl epoxystearate; polyester plasticizers, such as polyesters from a dibasic acid and a dihydric alcohol; polyethers, such as polypropylene glycol and derivatives thereof; polystyrenes, such as poly-a-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, chlorinated paraffin, and so forth may be used either singly or in combination in the form of a mixture of two or more of them, as desired. Favorable results are obtained when the plasticizer is used in an amount within the range of 0 to 100 parts by weight per 100 parts by weight of the reactive silicon group-containing oxypropylene polymer.
In using the reactive silicon group-containing oxypropylene polymer of the invention, various additives, such as tackifiers phenol resins, epoxy resins), adhesion improvers, physical property modifiers, storage stability improvers, antioxidants, ultraviolet absorbers, metal inactivators, antiozonants, light stabilizers, amine type radical chain 14 I I inhibitors, phosphorus-containing peroxide decomposing agents, lubricants, pigments, blowing agents, etc., may be added to said polymer as necessary each in an 4 appropriate amount to give room temperature curable compositions.
For further illustrating the invention, the following examples are given.
Example 1 A flask equipped with a stirrer was charged with 220 g (0.0447 equivalent) of polyoxypropylene triol having a number average molecular weight of 15,000 (Mw/Mn 1.38, viscosity 89 poises) and 0.02 g of dibutyltin dilaurate and, in a nitrogen atmosphere, 8.45 g (0.0447 equivalent) of y-isocyanatopropylmethyldimethoxysilane was added dropwise at room temperature. After completion of the dropping, the reaction was conducted at 750C for 1.5 hours. IR spectrum measurement was performed and, after confirmation of the disappearance of the NCO absorption at -1 about 2280 cm and of the formation of a C=0 absorption -1 at about 1730 cm the reaction was discontinued. A colorless and transparent polymer (213 g) was obtained.
Compartive Example 1 A 1.5-liter pressure-resistant glass reaction vessel was charged with 401 g (0.081 equivalent) of polyoxypropylene triol having a molecular weight of 15,000 (Mw/Mn 1.38, viscosity 89 poises) and the contents were placed under a nitrogen atmosphere.
At 137 0 C, 19.1 g (0.099 equivalent) of a 28% solution of sodium methoxide in methanol was added dropwise from a dropping funnel and the reaction was conducted for 5 hours. Then, the volatile matter was removed under reduced pressure. Again in a nitrogen atmosphere, 9.0 g (0.118 equivalent) of allyl chloride was added dropwise and the reaction was carried out for hours, and then the allylation was further conducted using 5.6 g (0.029 equivalent) of a 28% solution of sodium methoxide in methanol and 2.7 g (0.035 equivalent) of allyl chloride.
The reaction product was dissolved in hexane and the solution was subjected to adsorption treatment with aluminum silicate. After removal of the hexane under reduced pressure, there was obtained 311 g of a yellow and transparent polymer (viscosity 68 poises).
A pressure-resistant glass reaction vessel was Sj charged with 270 g (0.065 equivalent) of the above polymer and the contents were placed under a nitrogen atmosphere. After addition of 0.075 ml of a chloroplatinic acid catalyst solution (prepared by dissolving g of H 2 PtCl 6 *6H 2 0 in 500 g of isopropyl alcohol), j i r .1: 16 the mixture was stirred for 30 minutes. Dimethoxymethylsilane (6.24 g, 0.059 equivalent) was added from a dropping funnel and the reaction was carried out at 0 C for 4 hours. After volatile matter removal, there was obtained 260 g of a yellow and transparent polymer.
Comparative Example 2 I A pressure-resistant glass reaction vessel was i charged, after nitrogen substitution, with 420 g of polyoxypropylene glycol having a number average mole- I cular weight of 3,000 and 80 g of polyoxypropylene triol having a number average molecular weight of 3,000. After addition of 40 g of sodium hydroxide, the reaction was carried out at 60 0 C for 13 hours, then 19 g of bromochloromethane was added and the further reaction was conducted at 600C for 10 hours. (The polymer thus obtained had an Mw/Mn of 2.1 and a viscosity of 385 poises.) Then, 15 g of allyl chloride was added and the reaction was conducted for 36 hours. After completion Sof the reaction, the volatile matter was removed under reduced pressure.
The contents were transferred to a beaker, dissolved in hexane, and subjected to adsorption treatment with aluminum silicate, followed by removal of the hexane under reduced pressure.
i 17 '1, A reaction vessel was charged, after nitrogen substitution, with 500 g of said polymer, then 0.03 g of a chloroplatinic acid catalyst solution (prepared by dissolving 25 g of H 2 PtCl 6 *6H 2 0 in 500 g of isopropyl S2 6 2 alcohol) was added, thereafter 12 g of dimethcxymethylsilane was added, and the reaction was carried out at 0 C for 4 hours. After completion of the reaction, the volatile matter was removed under reduced pressure, whereupon 550 g of a pale-yellow, transparent polymer was obtained.
The viscosity of each of the polymers obtained in Example 1 and Comparative Examples 1 and 2 was determined at 23°C using a type B viscometer (BM type rotar No. 4, 12 rpm). Each polymer was also analyzed for number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) by GPC. The GPC was performed at an oven temperature of 40°C using a column packed with a polystyrene gel (Tosoh Corporation) and tetrahydrofuran as the eluent. The results are shown in Table 1.
18 Table 1 Viscosity Number average Molecular weight Polymer (poises) molecular weight distribution (Mn) (Mw/Mn) 4 Example 1 150 1.7 x 10 1.4 Comparative 88 1.8 x 104 Example 1 Comparative 380 1.8 x 104 2.3 Example 2 Example 2 and Comparative Example 3 One hundred (100) parts by weight of the polymer obtained in Example 1 or Comparative Example 1 was kneaded with 3 parts by weight of tin octanoate, part by weight cf laurylamine and 0.6 part by weight of water and the mixture was spread to give a sheet-like material, which was cured at room temperature for 2 days and further at 50°C for 3 days.
JIS No. 3 dumbbells were cut out from the cured sheets in accordance with JIS K 6301 and subjected to tensile testing for determining the tensile strength at break (TB) and elongation at break The results are shown in Table 2.
19 Table 2 Polymer used TB EB (kg/cm) Example 2 Example 1 5.2 140 Comparative Comparative 4.3 Example 3 Example 1 Example 3 and Comparative Example 4 One hundred (100) parts by weight of the polymer obtained in Example 1 or Comparative Example 1 was thoroughly admixed with 50 parts by weight of Epikote 828 (bisphenol 'A type epoxy resin produced by Yuka Shell Epoxy), 1 part by weight of Nocrac SP (monophenolic antioxidant produced by Ouchi Shinko Kagaku Kogyo), 5 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), 1 part by weight of N-p-(aminoethyl)-y-aminopropyltrimethoxysilane, 1 part by weight of #918 (organotin compound produced by Sankyo Yuki Gosei) and 0.4 part by weight of water.
The resultant mixture was poured into a polyethylene frame with care to prevent air bubbles from entering, and cured at 23°C for 2 days and further at 50°C for 3 days to give a cured sheet having a thickness of 2 mm.
No. 3 dumbbells were cut out from the thusobtained cured sheets in accordance with JIS K 6301 and subjected to tensile testing at a pulling rate of 500 mm/min. The results are shown in Table 3.
IIn the table, "M100" means the stress at 100% elongation, "TB" the tensile strength at break and "EB" the elongation at break.
Table 3 Polymer used M1002 T3 2 EB (kg/cm (kg/cm Example 3 Example 1 16 76 315 Comparative Comparative 14 38 235 Example 4 ExanTle 1 INDUSTRIAL APPLICABILITY As mentioned above, the reactive silicon groupcontaining oxypropylene polymer of the invention has a narrow molecular weight distribution despite its high number average molecular weight and therefore shows a lower viscosity, hence is easier to handle, before curing as compared with the conventional polymers having the same molecular weight and a broader molecular weight distribution.
The low viscosity before curing as mentioned above not only improves the processability but also enables incorporation of a large amount of filler to give an excellent room temperature curable composition.
After curing, the crosslinking network becomes 21 uniform and the cured products show good rubber-like elastic behaviors, for example improved elongation characteristics.
The polymer of the invention has a terminal urethane bond, so that the cured products after curing are excellent in strength and elongation.
Furthermore, the chemical resistance, for example acid resistance, is improved to an unexpectedly great extent. The water resistance is excellent as well.
Thus, the reactive silicon group-containing oxypropylene polymer of the invention is of very high practical value.
The production method of the invention is superior in that reactive silicon group introduction can be effected in one step without taking the complicated prior art reaction steps.
Compositions containing the reactive silicon group-containing oxypropylene polymer of this invention are particularly useful as elastic sealants and can be used as sealants for buildings, ships, automobiles, i roads, etc. Furthermore, said compositions, either as such or with the aid of a primer, can closely adhere to a wide variety of substances, such as glass, ceramics, wood, metals and resin moldings and therefore can be used as various types of sealing composition or 22- I adhesive composition. Furthermore, they are useful I also as food packaging materials, rubber materials for casting and materials for templating.
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Claims (4)
1. An oxypropylene polymer the main polymer chain of which is essentially composed of a repeating unit of the formula C H -CH-CH 2 -O- and which has at least one reactive silicon group and at least one urethane bond each terminally to said main chain and has an Mw/Mn ratio of not more than 1.5 and a number average molecular weight of not less than 3,000.
2. A method of producing reactive silicon group-con- taining oxypropylene polymers which comprises reacting an oxypropylene polymer having an Mw/Mn ratio of not more than 1.5 and a number average molecular weight per terminal functional group of not less than 1,500 with a compound having a reactive silicon group and an iso- cyanato group. i raa~~ larrP i I i 1 1 ABSTRACT This invention provides a novel reactive silicon group-containing oxypropylene polymer and a method of producing the same. The reactive silicon group-containing oxypropylene polymer of the invention is an oxypropylene polymer the main polymer chain of which is essentially composed of a repeating unit of the formula CH
3 CH CH 2 and which has at least one reactive silicon group and at least one urethane bond each terminally to the chain and has an Mw/Mn ratio of not more than 1.5 and a number average molecular weight of not less than 3,000. The production method of the invention is characterized by reacting an oxypropylene polymer having an Mw/Mn ratio of not more than 1.5 and a number average molecular weight per terminal functional group of not less than 1,500 with a compound having a reactive silicon group and an isocyanato group. 7 U1~-- C- INTERNATIONAL SEARCH REPORT International Application No PCT/JP91 00461 I. CLASSIFICATION OF SUBJECT MATTER (If several classification symbols apply, Indicate all) 6 According to International Patent Classification (IPC) or to both National Classification and IPC Int. C1 5 C08G65/32 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classlfictlon Symbols IPC i C08G65/02-C08G65/32 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched a Jitsuyo Shinan Koho 1926 1991 Kokai Jitsuyo Shinan Koho 1971 1991 III. DOCUMENTS CONSIDERED TO BE RELEVANT 9 Category Citation of Document, with Indication, where appropriate, of the relevant passages 2 Relevant to Claim No. 1 3 A JP, A, 61-141761 (Kanegafuchi Chemcial 1-2 Industry Co., Ltd.), June 28, 1986 (28. 06. 86), Line 3, lower left column to line 5, lower right column, page 1 EP, Al, 184829 US, A, 4837401 A JP, B2, 61-18582 (Kanegafuchi Chemical 1-2 Industry Co., Ltd.), May 13, 1986 (13. 05. 86), Lines 1 to 20, lower left column, page 1, line 38, left column to line 20, right column, page 2 (Family: none) A JP, A, 61-197631 (Kanegafuchi Chemical 1-2 Industry Co., Ltd.), September 1, 1986 (01. 09. 86), Line 5, lower left column to line 9, lower right column, page 1, lines 9 to 17, lower left column, page
4 EP, Al, 195951 US, A, 4654417 DE, B2, 3676326 Special categories of cited documents: 10 later document published after the International filing date or document defining the general state of the art which is not priority date and not In conflict with the application but cited to considered to be of particular relevance understand the principle or theory underlying the invention earlier document but published on or after the international document of particular relevance: the claimed invention cannot filing date be considered novel or cannot be considered to involve an inventive step document which may throw doubts on priority claim(s) or which is cited to establish the publication date of another document of particular relevance: the claimed invention cannot citation or other special reason (as specified) be considered to involve an inventive step when the document is combined with one or more other such documents, such document referring to an oral disclosure, use. exhibition or combination being obvious to a person skilled in the art other means other means document member of the same patent family document published prior to the International filing date but later than the priority date claimed IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report May 14, 1991 (14. 05. 91) May 27, 1991 (27. 05. 91) International Searching Authority Signature of Authorized Officer Japanese Patent Office Form PCT/ISA/210 (second sheet) (January 1985) im~maimpPCT/JP 9 1 00 46 1 CO 8G6 5/32 IPC CO 8G6 5/02-CO 8G6 5/32 Ei mw-flV* aw1 9 26- 19 91-4f 1 97 1- 19 9 MI. mAf5ai-7t;3Z A i ,A -141761 W TM-4 1-2 2 8. 6jj. 19 86 28. 0 6. 8 6) EP, A 1, 1 84 8 29 US, A, 48 37 40 1 A J PB21 18582(i- 2 1 3. 5JI. 1 98 6( 13. 0 5. 8 6) A J P. A, 6 1- 1 i76 3 1( A fitT1~*Ai- 2 1. 9)j. 1 9 86 (01. 0 9. 8 6). X~f-Mi7fi&EP. Al, 19 5951 &US, A. 4654417 &DE, B2, 3676326 9 W0 6 C~ 4JJ 8 01 MB uet~ft (ISA/JP);5 jt-~ j c 4mzt jo1 ;to FoC/1A2IC 2 191oO%
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9454390 | 1990-04-09 | ||
JP2-94543 | 1990-04-09 | ||
PCT/JP1991/000461 WO1991015536A1 (en) | 1990-04-09 | 1991-04-08 | Oxypropylene polymer containing reactive silicon group and production thereof |
Publications (2)
Publication Number | Publication Date |
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AU7575691A AU7575691A (en) | 1991-10-30 |
AU650872B2 true AU650872B2 (en) | 1994-07-07 |
Family
ID=14113231
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU75756/91A Expired AU650872B2 (en) | 1990-04-09 | 1991-04-08 | Oxypropylene polymer containing reactive silicon group and production thereof |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU650872B2 (en) |
CA (1) | CA2056363C (en) |
WO (1) | WO1991015536A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010008640A1 (en) * | 2008-07-16 | 2010-01-21 | Dow Global Technologies Inc. | Refrigerant compositions including silyl terminated polyalkylene glycols as lubricants and methods for making the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2995309B2 (en) * | 1991-09-09 | 1999-12-27 | 鐘淵化学工業株式会社 | Curable composition |
JPH07242737A (en) * | 1994-03-07 | 1995-09-19 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU614847B2 (en) * | 1988-06-10 | 1991-09-12 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition comprising and oxyalkylene polymer with reactive silicon groups and plasticizer |
AU7440991A (en) * | 1990-03-09 | 1991-10-10 | Kanegafuchi Chemical Industry Co. Ltd. | Curable composition containing silicon group-containing oxypropylene polymer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5273998A (en) * | 1975-12-16 | 1977-06-21 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing compositions |
JPS61141761A (en) * | 1984-12-12 | 1986-06-28 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
JPS61197631A (en) * | 1985-02-28 | 1986-09-01 | Kanegafuchi Chem Ind Co Ltd | Production of polyalkylene oxide of narrow mw distribution |
-
1991
- 1991-04-08 CA CA002056363A patent/CA2056363C/en not_active Expired - Lifetime
- 1991-04-08 AU AU75756/91A patent/AU650872B2/en not_active Expired
- 1991-04-08 WO PCT/JP1991/000461 patent/WO1991015536A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU614847B2 (en) * | 1988-06-10 | 1991-09-12 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition comprising and oxyalkylene polymer with reactive silicon groups and plasticizer |
AU7440991A (en) * | 1990-03-09 | 1991-10-10 | Kanegafuchi Chemical Industry Co. Ltd. | Curable composition containing silicon group-containing oxypropylene polymer |
AU7485991A (en) * | 1990-03-09 | 1991-10-10 | Kanegafuchi Chemical Industry Co. Ltd. | Curable composition containing silicon group-containing oxypropylene polymer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010008640A1 (en) * | 2008-07-16 | 2010-01-21 | Dow Global Technologies Inc. | Refrigerant compositions including silyl terminated polyalkylene glycols as lubricants and methods for making the same |
Also Published As
Publication number | Publication date |
---|---|
CA2056363C (en) | 1999-06-01 |
CA2056363A1 (en) | 1991-10-10 |
WO1991015536A1 (en) | 1991-10-17 |
AU7575691A (en) | 1991-10-30 |
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