WO1991015536A1

WO1991015536A1 - Oxypropylene polymer containing reactive silicon group and production thereof

Info

Publication number: WO1991015536A1
Application number: PCT/JP1991/000461
Authority: WO
Inventors: Masayuki Fujita; Michihide Homma; Hiroshi Wakabayashi
Original assignee: Kanegafuchi Chemical Industry Co., Ltd.
Priority date: 1990-04-09
Filing date: 1991-04-08
Publication date: 1991-10-17
Also published as: AU650872B2; AU7575691A; CA2056363A1; CA2056363C

Abstract

A novel oxypropylene polymer containing a reactive silicon group, wherein the main polymer chain essentially comprises the repeating units of formula (α), at least one reactive silicon group and at least one urethane bond are present at the terminals of the polymer chain, the ratio of M^¨B7w to M^¨B7n 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 of M^¨B7w to M^¨B7n of 1.5 or less and a number-average molecular weight per unit terminal function of 1,500 or above with a compound having both a reactive silicon group and an isocyanate group.

Description

Oxidative propylene polymer containing reactive silicon group and process for producing the same

[Technical Field] The present invention relates to a novel oxypropylene polymer containing a reactive silicon group and a method for producing the same.

[Background Art] Conventionally, various kinds of room-temperature-curable polymers that can be cured into a rubber-like substance by moisture have been developed, and a reactive silicon-based polymer has been developed. (A group containing a silicon atom to which a hydroxyl group or a hydrolyzable group is bonded and which can form a siloxane bond) Oxypropyl propylene polymers are also known

However, conventionally, it has been difficult to produce high molecular weight polyoxypropylene, which has a narrow molecular weight distribution (high monodispersity), and thus has a high reactivity. Polyoxypropylene containing a basic group has not been known as a polymer having a wide molecular weight distribution (high polydispersity).

Recently, it has been reported that polyoxypropylene having a narrow molecular weight distribution can be obtained. The present inventors have found that a polymer having a narrow chain of polyoxypropylen as a main chain and having a reactive gayene group and a urethane bond introduced at its terminal is cured. Before you The present invention was found to be low in viscosity and easy to handle, and that the cured product after curing had not only excellent tensile properties, but also chemical resistance and water spraying properties.

[Disclosure of the Invention] The reactive siloxane-containing oxypropylene polymer of the present invention essentially has a polymerizable polymer.

^CH _S type 1 CHCH 1 0

An oxypropyne having at least one reactive GA group and at least one urethane bond at each end, consisting of a return unit represented by It is a ren polymer, having a MwZMn force of 1.5 or less and a number average molecular weight of 3,000 or more.

In addition, the production method of the present invention can be used with MwZMnforce <1.5 or less.

An oxypropylene polymer having a number-average molecular weight of 1,500 or more per terminal functional group, and a reactive silicon group and an isocyanate group Characterized by reacting with a compound having

[Best Mode for Carrying Out the Invention] The reactive gating group according to the present invention is not particularly limited, but typical examples thereof include those represented by the following general formula: The group represented by (1) is mentioned. One X a (1)

[In the formula, your good beauty R ² a are both § Ruki Le group having from 1 to 2 0 carbon atoms, the number of al-2 0 of § Li Lumpur based on carbon, the number of carbon atoms? ~ 2 0 § La alkyl group or a (R ') 3 S i O - shows the door the Rio Ruga Bruno filtered off key sheet group is Ru are shown in, were R ¹ or R ² is 2 or more When they are present, they can be the same or different. Here, R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a indicates 0, 1, 2 or 3, and b indicates 0, 1 or 2. Also, m

R 1

2-b

-S i-0-

The b in X b may be different. m represents 0 or an integer of 1 to 19. However, a + ∑b1 shall be added. The hydrolyzable group represented by X is not particularly limited, and may be any conventionally known hydrolyzable group. Specifically, it is known that a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, Acid amide groups, aminooxy groups, menolecapto groups, alkenyloxy groups, and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, and an aminooxy group are included. Groups, a mercapto group and an alkenoxy group are preferred, but an alkoxy group is particularly preferred from the viewpoint of mild hydrolyzability and easy handling.

This hydrolyzable group or hydroxyl group can be bonded to one to three silicon atoms, and (a + ∑b) is preferably 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are present in the reactive silicon group, they may be the same or different.

The reactive silicon group may have one or more than two silicon atoms, but the connection of the silicon atoms by siloxane coupling or the like. In the case of the provided reactive silicon group, about 20 groups are preferable.

Incidentally, a reactive silicon group represented by the following general formula (2) is preferable from the viewpoint of easy availability.

K 3 -a

I ...... (2)

One si - x _a

(Where RX and a are the same as above.) In addition, specific examples of R ¹ and R ^{2 in} the general formula (1) include, for example, alkyl groups such as a methyl group and an ethyl group, and cycloalkyl groups. Cycloalkyl groups such as xyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, R'methylol groups and phenyl groups And a triorganosiloxane group represented by (R ′) ₃ Si 0 —. Of these, a methyl group is particularly preferred.

It is preferred that at least one, preferably 1.1 to 5 reactive silicon groups be present in one molecule of the oxypropylene polymer. If the number of reactive silicon groups contained in is less than one, the curability becomes insufficient and good rubber elasticity behavior is hardly exhibited.

There is at least one reactive gay group at the terminal of the oxypropylene polymer molecular chain, but it may be present inside. As in the present invention, when the reactive silicon group is present at the terminal of the molecular chain, the effectiveness of the oxyprovirene polymer component contained in the finally formed cured product can be improved. The increased number of mesh chains makes it easier to obtain a rubber-like cured product that exhibits high strength and high elongation (low elastic modulus).

The urethane bond in the present invention is a bond represented by one NHCOO—.

The oxyprovirene polymer constituting the polymer main chain in the polymer of the present invention is essentially

^CH 3 formula CH-CH 2 0 1

It consists of the return unit indicated by. This phone One —

The propylene polymer may be in the form of a straight line, in the form of a branch, or in a mixture thereof. Further, a small amount of other monomer units may be contained.

As the number average molecular weight of this oxypropylene polymer, one having a molecular weight of 3,000 or more can be effectively used, but preferably, the one having a linear shape is preferred. The polymer having a molecular weight of 3,000 or more and the branched one is preferably 5,000 or more. More preferably, it has a number average molecular weight of 6,000 to 30,000. In addition, the ratio of heavy S-average molecular weight to number-average molecular weight (^ iw ZM n) of this oxypropylene polymer is not more than 1.5, and the molecular weight distribution is extremely narrow. (Large monodispersity). The value of i¾wZMn is preferably less than or equal to 1.4, more preferably less than or equal to 1.3. Although the molecular weight distribution can be measured by various methods, it is generally measured by a gel permeation chromatography (GPC) method. As described above, although the number average molecular weight is large, the molecule; a, the distribution of which is narrow, so that the polymer of the present invention has low viscosity before curing and is easy to handle, and after curing, Shows good rubber-like elastic behavior.

Further, in the polymer of the present invention, since a urethane bond is also present at the terminal, the cured product after curing has excellent strength and elongation.

In order to produce the reactive silicon group-containing oxyprovirene polymer of the present invention, an oxoprovirene polymer having a functional group such as a hydroxyl group at its terminal (hereinafter referred to as Y functional group) is used. The propylene polymer may be reacted with a compound having an isocyanate group and a reactive silicon group that are reactive to the Y functional group. .

As the oxypropylene polymer having this Y functional group, M w ZM n is 1.5 Ru have use the following 1 1 terminal functional Mototo Ri having a number average molecular, 5 0 0 or der Ru O key sheet profile pin les down polymer ₀

In addition, compounds having an isocyanate group and a reactive silicon group include, but are not limited to, an isocyanate-propynolate triethoxysilane. , Key-isolated-protocol-measurement xylan, key-isolated-prototype-measurement xylan, etc. Such silane-containing silanes are not limited to these powerful and specific examples.

Thus, an oxypropylene copolymer having a Y functional group at the terminal is reacted with a compound having an isocyanate group and a reactive silicon group. According to the production method of the present invention, a reactive gay group can be introduced in one step without going through a complicated reaction step as in the prior art.

The reactive oxypropylene polymer containing a reactive silicon group of the present invention forms a three-dimensional network by exposure to the air, and is a rubber It hardens to an elastic solid.

In curing the polymer of the present invention, a silane condensation catalyst (curing catalyst) may or may not be used. In the case of using a silane condensation catalyst, those conventionally known can be widely used. Specific examples thereof include titanic acid esters such as tetrabutyl titanate, tetrabutyl titanate, etc .; Suzukanolevo, such as Laurate, Djibutinoles Maleate, Djibutinoresuzujiacetate, Succinooctylate, and Naphthenate Reaction products of dibutyl sulphoxide and diester phthalate; dibutyl sul diacetyl acetonate; aluminum Tri-Secire Nore Settlement, Anominator Trim Settlement Attached Jig Soproxy Numoret Minimati Seta Organic aluminum compounds such as thiocyanate; zirconium tetracetinoacetyl acetate; titantra acetic acid acetate; Chelate compounds such as; lead octylate; petitlamin, octylamine, dibutynoleamine, monoethanolamine, dietone Tanoremin Amin, Triethanolamine Amin, Diethylentriamine, Triethylene Tramin, Oleamine, Cyclohexamine, Penginolemin, Jetinomininopropinomine, Kisiri Ranges, triazines, guanidines, diphenyl guanidines, 2,4,6-tris (dimethylamines) Minenomethyl) phenol, morpholin, N-methylmorpholin, 2-ethyl-4-methyl-imidazole, 1, 8 -Aminic compounds such as diazabicyclo (5.4, 0) decen-7 (DBU), or carboxylic acids of these aminic compounds such as carboxylic acid A low-molecular-weight polyamide resin obtained from an excess of polyamine and a polybasic acid; a reaction product of excess polyamine and an epoxide compound; N- (8—Amino-ethyl) N- (8-Amino-ethyl-methyl) Amino group Silane coupling agents, such as silane coupling agents, and other known silane coupling catalysts, such as other acidic catalysts and basic catalysts. It is terrible. These catalysts may be used alone or in combination of two or more.

The amount of the silane condensation catalyst used is preferably about 0.1 to 20 parts by weight based on 100 parts by weight of the oxypropylene polymer. About 10 parts by weight is more preferable. Oki If the amount of the silane-condensation catalyst used is too small relative to the propylene polymer, the curing speed becomes slow; and the curing reaction does not proceed sufficiently. Is not preferred. On the other hand, if the amount of the silane-condensation catalyst used is too large relative to the oxipone pyrene polymer, local heat generation and foaming occur during curing, and a good cured product is obtained. I don't like it because it makes it difficult to obtain.

The reactive silicon group-containing oxyprovirene polymer of the present invention can be modified by incorporating various fillers. As fillers, fumescent silica, settling silica, reinforcing fillers such as anhydrous ganoic acid, hydrous ganoic acid and carbon black; carbonic acid Calcium, magnesium carbonate, silicate clay, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite Fillers such as it, ferric oxide, zinc oxide, active zinc white and silica balloon; fibrous materials such as asbestos, glass male fibers and filaments Fillers can be used.

When a high-strength cured composition is to be obtained with these fillers, it is mainly necessary to use fumed silica, sedimentable silica, gay anhydride, hydrated caic acid, and carbon. Fillers selected from black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc white are used to form reactive oxygen-containing oxypros. Preferable results can be obtained if the amount is in the range of 1 to 100 parts by weight based on 100 parts by weight of the pyrene polymer. In order to obtain a hardened composition having low strength and large elongation, mainly titanium oxide, calcium carbonate, magnesium carbonate, and talc are used. A filler selected from the group consisting of iron oxide, ferric oxide, zinc oxide, and silica balun is added to 100 parts by weight of the reactive silicon-containing oxypropylene polymer. Good results are obtained when used in the range of 5 to 200 parts by weight. . Of course, these fillers may be used alone or in combination of two or more.

When using the reactive gypsum group-containing oxyprovirene polymer of the present invention, when a plasticizer is used in combination with a filler, the elongation of the cured product is greatly increased. It is more effective because it can mix a large amount of filler. This plasticizer is one that is commonly used. For example, esters of phthalanolic acid such as dioctyl phthalate, dibutynophthalate, butynol benzyl phthalate; adivin Aliphatic dibasic acid esters such as dioctynoleic acid, kono, isodecyl citrate and dibutyl sebacate; diethyl glycol Benzoates, pentaerythritol, and other polyesters, such as glycol esters; butyric acid oleate, acetyl acetylene resin Aliphatic esters such as methyl phosphate; triglyceryl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc. Esters of phosphoric acid, such as epoxidized soybean oil, and epoxies, such as epoxidized stearate benzyl. Plasticizers; Polyester plasticizers such as polyesters of dibasic acid and divalent alcohol; Polypropylene glycols and the like. Polystyrenes such as derivatives of polystyrene; polyα-methylstyrenes, polystyrenes such as polystyrenes; polybutadienes, butylenes Tadiene acrylonitrile copolymer, polyclonal plate, polyisoprene, polybutene, chlorinated paraffin, etc. The plasticizer can be optionally used alone or in the form of a mixture of two or more. It is preferable to use the plasticizer S in an amount of 0 to 100 parts by weight based on 100 parts by weight of the reactive propylene group-containing oxypropylene polymer. Is obtained. In using the reactive propylene group-containing polymer of the present invention, if necessary, a phenol resin and an epoxy resin may be further used. Resin and other adhesion-imparting agents, adhesion improvers, physical conditioners, storage stability improvers, anti-aging agents, ultraviolet absorbers metal deactivators, ozone deterioration inhibitors, light stabilizers, amines A room temperature curable composition can be obtained by appropriately adding various additives such as a system-based radical chain inhibitor, a phosphorus-based peroxide decomposer, a lubricant, and a pigment foaming agent.

Examples In order to further clarify the present invention, examples will be given below.

Example 1

A polycarbonate with a number average molecular weight of 15,500 was added to a flask with a stirrer (wZKin-1.38, viscosity 89%). 2) 0: (0.0447 equivalents) and 0.02 g of dibutyltin dilaurate were charged, and the solution was dissolved under nitrogen atmosphere. 8.45 g (0.0444 equivalents) of propylmethyldimethoxysilane was added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 75 ° C for 1.5 hours. After measuring the IR spectrum and confirming the disappearance of the NCO absorption near 2280 cm "" ¹ and the generation of C »0 absorption near 1730 cm— ¹ , the reaction was terminated. Was. 213 g of a colorless and transparent polymer were obtained.

Comparative Example 1

1.5 J? Polyoxypropyl phenol with a molecular weight of 15,000 (SiwZn-1.38, viscosity: 89,9 V) in a pressure-resistant glass reaction vessel 4) 1 g (0.081 equivalent) was charged and the atmosphere was kept under nitrogen atmosphere.

At 1 3 7, 2 8 of sodium medex % Methanol solution: 19.1 g: (0.099 equivalent) was added dropwise, and the mixture was reacted for 5 hours. After returning to the nitriding atmosphere, 9.0 & (0.118 equivalent) of aryl chloride was added dropwise, and after reacting for 1.5 hours, sodium methoxide was further added. 5.6 g (0.029 eq.) Of 2.8% methanol solution and 2.7 g (0.035 eq.) Of aryl chloride are used to carry out the arylation. O

After dissolving this reaction product in hexane and adsorbing it with aluminum gumate, the hexane was decompressed and removed to obtain 311 g of a yellow transparent polymer. Was obtained (viscosity: 68 vise).

270 g (0.065 equivalents) of this polymer was charged into a reaction vessel made of a pressurized glass and placed under a nitrogen atmosphere. The catalyst solution _{_{(H 2 P t C £ 6}} · 6 H 2 0 2 to 5 s and melt-in Lee Seo profile Birua Honoré co Lumpur 5 0 0 g solution) of chloroplatinic acid 0. 0 7 5 m £ After the addition, the mixture was stirred for 30 minutes. 6.24 g (0.059 equivalent S) of dimethoxymethyllane was added from a dropping funnel, reacted at 90 for 4 hours, and then devolatilized. A 0 s yellow transparent polymer was obtained.

Comparative Example 2

Polyoxypropylene glycol with a number average molecular weight of 3,000 0 4 0 g and a polyoxypropylene propylene with a number average molecular weight of 3,000 80 g of the triol was charged into a pressure-resistant glass reaction vessel in which nitrogen was replaced. After adding sodium hydroxide (40 s), the mixture was reacted at 60 for 13 hours, and then, the reaction of bromochlormethane 1 was performed at 60 for 10 hours. (The obtained polymer had an iw ZKin of 2.1 and a viscosity of 38.5 voices.) Then, 5 g of L: L was added, and the reaction was carried out for 36 hours. After the completion of the reaction, the pressure was reduced to remove the volatile substances.

The contents were taken out into a beaker and dissolved in hexane. After adsorption treatment with aluminum gaymate, the hexane was depressurized and removed.

This port Li Ma -5 0 0 8: only charged to a reaction vessel which is nitrogen S conversion, catalyst solution _{_{(H 2 P t CQ 6 ·}} 6 H 2 0 2 5 g of Lee Seo-flop of chloroplatinic acid b After adding 0.03 g, add 12 g of dimethoxymethane, add 12 g of dimethoxymethane, and incubate at 80 for 4 hours. Reacted. After completion of the reaction, the pressure was reduced and the volatile substances were removed to obtain 550 g of a pale yellow transparent polymer.

The viscosities of the polymers obtained in Example 1 and Comparative Examples 1 and 2 were measured using a B-type viscometer (BM type rotor No. 4, 12 rpm). Measured in 23. The number average molecular weight (Mn) and molecular weight distribution (MwZn) of each polymer were analyzed by GPC. GPC uses tetrahydrofuran as a distilling solvent for a column filled with polystyrene gel (manufactured by Tosoh Ichi Co., Ltd.), and prepares an open plate. The analysis was performed at a temperature of 40 ° C. Table 11 shows the results. 4 one

Table

Example 2 and Comparative Example 3

To 100 parts by weight of the polymer obtained in Example 1 or Comparative Example 1, 3 parts by weight of octyl acid, 0.5 part by weight of raurilamin, and water 0.6 parts by weight were kneaded, stretched in a sheet form, and then cured at room temperature for 2 days and further at 50 at 3 days.

The sheet strength of the cured product was punched out from a JIS No. 3 dumbbell based on JISK 6301 and a tensile test was performed to determine the strength at break (TB) and elongation at break (EB ) Are shown in Table 1-2. 5 one

Table 1 2

Example 3 and Comparative Example 4

To the polymer 100 parts by weight obtained in Example 1 or Comparative Example 1 was added Ebicoat 828 (a bisulfate-based epoxy resin bismuth). 50 parts by weight, Nocrack SP (Monofunol antiaging agent manufactured by Ouchi Shinko Chemical Co., Ltd.) 1 part by weight, 2, 4, 6-tris (dimethylaluminum) phenol (DMP-30) 5 parts by weight, N-β

(Amino Ethyl) 1 part by weight of Amino Blobinole Trimethoxysilane, # 9 18 (1 part by weight of organotin compound manufactured by Sankyo Seiki Co., Ltd.) After thoroughly mixing 0.4 parts by weight of water, pour carefully into the polystyrene mold to prevent air bubbles, and use 2 3 for 2 days. The mixture was further cured for 3 days at 50 to obtain a cured product sheet having a thickness of 2 ma.

A No. 3 dumbbell was punched out in accordance with the sheet force of the cured product and JJIS 6301, and a tensile test was performed at a tensile speed of 500 minutes. Table 1 shows the results.

In the table, M 100 is the stress at 100% elongation, and Τ 破 is the fracture. Shear strength, EB indicates elongation at break

1

6

[Industrial Applicability] As described above, the reactive oxy-propylene polymer containing a reactive silicon group of the present invention has a high molecular weight even though its molecular weight is large. Since the molecular S distribution is narrow, before curing, compared to a conventional polymer having the same molecular S and a wide molecular weight distribution, the viscosity is lower and the handling is valley ^ 7C.

Since the viscosity before curing is low as described above, not only workability is good, but also a large amount of filler can be blended to obtain an excellent room temperature curable composition.

After hardening, it shows good rubber-like elastic behavior such as a uniform cross-link network and improved elongation characteristics.

Further, since the polymer of the present invention has a urethane bond at a terminal, a cured product after curing has excellent strength and elongation.

Furthermore, chemical resistance, such as acid resistance, is unexpectedly greatly improved. 1] 7 —

It is also excellent in water resistance.

As described above, the reactive silicon group-containing oxyprovirene polymer of the present invention has extremely high practical value.

In addition, the production method of the present invention is an excellent method that can introduce a reactive silicon group in one step without having a complicated reaction step as in the prior art. It is.

The composition containing the reactive silicon-containing oxyprovirene polymer of the present invention is particularly useful as an elastic sealant, and can be used for buildings, ships, automobiles, roads, and the like. Which sealant to use. In addition, it can adhere to a wide range of substrates, such as glass, porcelain, wood, metal, and resin moldings, alone or with the help of the primer, so that various types of substrates can be used. It can also be used as a sealing composition and an adhesive composition. Furthermore, it is also useful as a food packaging material, a casting rubber material, and a molding material.

Claims

8 Scope of Claim

1. Polymerization is essentially

CH 3 formula Consists of a repeating unit represented by CH-CH-0-, and has at least one reactive gay bond group and at least one urethane bond at its terminal. An oxypropylene polymer having a w / ϊπ force of 1.5 or less and a number average molecular weight of 3,000 or more, which is a propylene propylene polymer.

2. an oxypropylene copolymer having a MwZn of 1.5 or less and a number-average molecular weight per terminal functional group of 1,500 or more;

A compound having a reactive gating group and a compound having an isocyanate group is used.

A method for producing a reactive gypsum group-containing oxyprovirene polymer, which is characterized by reacting.