JPS58122918A - Production of novel polyether - Google Patents

Abstract

PURPOSE:To produce a high-MW polyether, by copolymerizing glycidol with a three-membered ring epoxide in the presence of a specified catalyst. CONSTITUTION:A catalyst is obtained by heating, with stirring, an organotin compound of one of formulasI-V, wherein R is a hetero atom-containing 1-12C aliphatic or aromatic hydrocarbyl group which may be substituted; X is H, a halogen, hydroxy, an alkoxy, an aryloxy or an acyloxy; a is 1-4, R' is R or X and at least one R' is R; X' is a carbonate group, a P-containing oxyacid residue, a polybasic acid group, a polyhydric alcohol residue; c is a number >=1 and is equal to the basicity of X'; d is 1 or 2 and e=3/2 when d=1; and e=1 when d=2; f is a positive integer; L and L' are each O or a group of formula VI; M is an (un)saturated hydrocarbyl and g>=1; together with a fully or partially esterified product of a P-containing oxyacid of one of formulas VII-IX, wherein Z is an aromatic group. Then, glycidol is copolymerized with a three-membered ring epoxide in the presence of this catalyst.

Description

[Detailed description of the invention]

The present invention relates to a method for producing high molecular weight polyethers having hydroxy groups in the molecule by copolymerizing glycidol (1,2-xoxy-3-hydroxypropane) with other 1,2-alkylene oxides. Conventionally, a large number of ring-opening polymerization methods have been disclosed for the production of polyethers by polymerizing three-membered ring epoxides, but generally known catalyst systems contain active hydrogen such as hydroxyl groups. Polymerization of monomers could not be carried out. For example, a typical high polymerization catalyst for three-membered ring epoxide, such as a catalyst system mainly composed of an organometallic member of Group 1 or liquid 1 of the periodic table, reacts directly with active hydrogen and loses its catalytic activity. Furthermore, for many cationic or anionic catalysts that produce low molecular weight polyethers, alcohols act as polymerization inhibitors or chain transfer agents, making it impossible to achieve the desired polymerization reaction. The present invention utilizes a reaction product obtained by heating an organotin compound and a phosphoric acid ester, which the applicant has already disclosed as a ring-opening polymerization catalyst for three-membered epoxide (U.S. Pat. No. 3,773,694). The present invention is based on the discovery that glycidol acts effectively as a catalyst in the copolymerization of glycidol with other three-membered epoxynides. Another object of the present invention is to provide a method for producing polyethers having hydroxy groups in their molecular chains that can be used in modification reactions or are effective in modifying physical properties such as hydrophilic properties of polymers. The object of the present invention is to provide a method for obtaining novel polyethers having hydroxyl groups that can be used as raw materials for components such as polyurethane.That is, the present invention provides a method for obtaining novel polyethers having hydroxyl groups that can be used as raw materials for components such as polyurethane. Ra5nX-a (I) (However,
In the above formula (I), R is an aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms, and these groups may have a substituent containing a hetero atom. Further, when a=2 or more, R may be the same or different. X is a group selected from a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, and an acyloxy group, and the X's where a=2 or 1 may be the same or different. a6- is an integer from 1 to 4. ) (RiSn)cX' (I[) (However, in the above formula (I), R' is

A group selected from the group of R and X, and at least one of R' is R. X' is a group selected from the group consisting of carbon MM, phosphorus oxygen acid group, polybasic carboxylic acid group, and polyhydric alcohol residue. C is a number greater than 1 corresponding to the basicity of X'. ) Rd S+ Oe (I[) (However, in the above formula (I), R is the same as R in formula (I). d is 1 or 2, and the end of d = 1 e =
3/2, d=2 and o=1. Further, the compound of formula (I[[) may form a complex with the compound of formula (I). ) -R'÷R2511-0 Sll R2-R' (I
V) (However, in the above formula (IV), R is the same as R in [) in formula (I>), and R' is the same as R' in formula (I). is a positive integer. ÷R23n -L M L' h (V) (However, in the above formula (V), R is a positive integer.
is the same as , and L or barb is an oxygen atom or O II 11 10-0-, and in the case of -C-O-, M is a group bonded with carbon. L and B may be the same or different. M is a saturated or unsaturated hydrocarbon group. , g1. This is a larger number than tI. ) and a compound represented by the following general formulas (VI) to (■), (1-10) 3 P=O(Vl) (HO) 2 P -0-P (01-1> 2 (V
IA) 11(1 0 Z-P(01-1>2 (■)1 (However, in the above formula (■), Z is an aromatic group.) Group J: selected phosphorus oxygen acids Novel polyethers are produced by copolymerizing glycidol and three-membered epoxylide, which is characterized by mixing and heating the complete or partial esterified product (B) of glycidol and one or more completely or partially esterified products (B), and using the reaction product as a catalyst. In the present invention, the following can be mentioned as specific examples of the organic tin compound which is the component (A).As the compound belonging to the above general formula (I), (C21-
1s) 43m, (C4Hs) 43m. (a(2=(]() 43w, (C3H7) s
S++H. (013) 3 S++F, (C4to1
y) 3 5TIF. (C21-1s) 3 S++(χ2.(C4H
])333mX2゜(Dls)(Ca Hi
) 2'a(A. 9- (O(3)33nBr, (Cg l-117>33
nl. (C) (3) 2 SnF? ,
(C4F+?) 2 3u(A 2(Cu
t-12ri 2 5nl13r2. (cycle. CA Hu) 2 Sn (χ22,
(C4H]) 511F3. (C8Ht7) 5Trails, (C21-
1s) 5nBr3゜(04Ha) 33nOC
4Ht. (Cg l-417>s 5nOQ](H3゜1 10-) As a compound belonging to the above general formula (II), [(aI
3) 33n32G] 3゜[(C41-1t) 3Sn] 2 (sword 3゜((,
4t-1te)3310P(0)(QC81-117)
2. [(C81-117) 33n13 PO4. (C41-ly) 3 5TIOQ12 0(2
03m(04t1?)3, [(C41-
1 ) 2 ([) (30) Sn-0 (140 (2) 4
．． -0CI)-3n (OQ(3)(C4+-1?)
2. -f ()12-(li (Polymcr) , the total vignetting is GOO3TI (C41-1?) 3. Compounds belonging to the above general formula (I[I) are ((]
-A1) 2 SnO, (04+-1?) 23n
O. (Cg l-1+7) 2 SnO, (Cb 1-Is
) 2 SnO. Od3SI1gh, C41-1t5nOh, I1, etc., and examples of complexes of compounds of general formula (I) such as general formula (I), (O12)23uO.(021-1s)2Sn
[3rz. (Q(3) 2 SnO・(C13) 2 S++Qh
. Q(3[(Q(3) 2 SnO] A20013 ・
(G(3) 2 SnBr2.) Examples of compounds belonging to general formula NV include (O(3)
) 33TIO3I+ ((L) 3° mark (C41-
1? ) 25nO3n (C41-1? ) (2). (013Coo) Cb IIs 5nO3n (C
41-1s)(0(3COO)), etc. Compounds belonging to general formula (V) represented by -F can be exemplified. Alternatively, specific examples of partially esterified products include the following: (013) 3 PO4, (C21-1s) 3
PO4. (Cs 1-17) s PO4, (C
4Hte)3PO4゜(Cg H+7 > 3
I)04, (C12H2ra)3PO4°N] (2=04-1]42) 3PO4. ((n(12-Q10) s PO4. (12C31-Is) 3 PO4. (C2l-l5) 2 1-IFY]4. . (C41-17) 2 1-IFte) 4. (C4,l -1 t) l-12 yen 4° (C4 day t
)4P207゜(C41-1t) 2 1-12 P2 07
. (C41-Is) (C31-h O) 2
PO85 In the present invention, the component (B) constituting the catalyst is:
Even if a combination of component compounds capable of forming (B) is directly added to the catalyst production reaction system together with component (A), a catalytic reaction product having a similar catalytic action can be obtained. Examples of the silk mixture U of component compounds that can form such component (B) include (a) A4: Shiha "1 phosphorus genide, an alcohol having a base number of 1 to 12, and Combination "(b) A phosphorus oxygen acid selected from the above general formula (1 to (■)) or a partial esterified product thereof and A-refins having 2 to 12 carbon atoms, alcohols having 1 to 12 carbon atoms, or Eboki (c) combinations with phosphoric anhydride and alcohols having 1 to 12 carbon atoms, etc. Examples of the phosphorus oxyhalide mentioned in (a) above include: POQI3. POBr3. POIs. ' (C2Hs O) P (0) CIl. 14- (Cg 1i170 ) 2 F) (0) Br etc. Examples of alcohols include 0(30H. C21- 1s Off, C3l-1? Gl,
C4Hte [l(. CA l-113DH, (℃012-012 DH,H
OC) (2-0120H etc. is an example of Eboki → Noids, and an example of A Refine is C21-14,, C3l-I A. O12=C(Oh ) 2 , (l12=(1)-(
1) 2cIl. Examples include 0(2=(11-(O12) 3-G(3). C) to a3+norfu1 ((as water phosphoric acid, P2
O3 is the best. Examples of alcohols include those mentioned in (a) above. The catalyst used in the present invention is usually heated at 100 to 300°C (
It is produced by mixing and heating the A> component and the (B) component or the (Δ> component and a combination of component compounds capable of forming the (13) component).A solvent may be used if necessary. MoJ: Yes. Components (A) and (B) are used so that the ratio of tin atoms to phosphorus atoms that are normally contained is in the range of 1:10 to 10:1. The catalytic reaction product obtained by the reaction is a variety of relatively simple substances that are produced and de-1ized in a condensation reaction, depending on the type of components.The resulting composite exhibits the desired activity at various stages of the degree of condensation. The optimum degree of condensation varies depending on the type and ratio of components (A) and (B), but they can be easily determined experimentally. Although it is soluble in solvents such as , hekirin, and benzine, it becomes insolubilized as the condensation reaction progresses. Specific examples of the three-membered ring ebokylide that is a copolymerization monomer component in the present invention include , ethylene oxide 1:'1 nod, pyrene oxy 1 nod, 1-butene oxide 1J ide, butadiene monooxide, sudylene Δ2 1:1J
1,2-al:1-sinoquinoids such as ido, epichlorohydrin. shrimp [1] Shrimp halohydrins such as muhydrin, glycidyl ethers such as phenyl glycidyl ether, propyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate,
Glycidyl esters such as glycidyl propionate 4
Examples include T. In the practice of the present invention, the copolymerization reaction is usually carried out in the fA range of 10 to 80°C in the presence or absence of a solvent. Catalyst is 0.01-1.0 per 100g of total monomers
A range of g is appropriate. Preferable results are obtained by keeping the water content in the copolymerization reaction system as low as possible. In order to obtain a homogeneous copolymer, 17- is subjected to conventional means such as stirring or wall separation. The organotin-phosphate ester reaction product catalyst used in the present invention generally provides a crystalline polyether in the polymerization of 1,2-evokylide. Therefore, crystalline polyhydroxy polyether can be obtained by adding a small amount of glycidol. Also, two or more types of T
Copolymerization of hoquinoids at an appropriate ratio of 27 (') gives a rubber-like polyether. Therefore, by further adding a small amount of glycidol as a third component to this system, a rubber-like polyether having hydroxyl groups can be obtained. In the present invention, polymerization with glycidol generally decreases the molecular weight as the proportion of glycidol increases.However, by adjusting the amount, the object of the present invention can be The ratio of glycidol as a 7-mer composition in the polymerization system varies depending on the intended use of the resulting polymer. 15 mol % or less yields the generally preferred target product.The polyhydroxy polyether obtained by the present invention can be di- or poly]nibo-4nylide, di- or poly It can be crosslinked by polyfunctional compounds that react with hydroxy groups, such as isocyanates, di- or polycarboxylic acids or anhydrides, or polyhalides. It can also be crosslinked with halogen-containing monomers such as epic[1] hydrin and glycidol. By heating in the presence of an acid acceptor, the copolymer can be crosslinked without adding a special crosslinking agent.Also, the commonly known chemical reaction carried out by the hydroxyl groups of alcohols A similar reaction can be carried out under appropriate conditions.The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.Example 1 Stirrer and temperature Piece 1: Put 80 g of tribudyltin chloride and 1-133 g of tributyltin chloride into a Mitsuro flask equipped with a small distillation apparatus, and heat to 240°C while stirring under a nitrogen stream, and at that temperature The distillate was distilled out by holding for 1 minute, and the residue was made up of about 100% of the "C" catalyst material.
I got 1. After washing with hexadiamine, it was dried under vacuum and stored in a desiccator. The carbon content of this material according to elemental analysis was approximately 32%. Epichlorohydrin and glycidol were copolymerized using the above product as a catalyst. The above ts50T119 was placed in a polymerization test tube, heated at 160°C for 20 minutes under a nitrogen stream to dehumidify it, and after cooling to room temperature, 9.4 g of epichlorohydrin and 0.4 g of glycidol were added.
2 g (5.3 mol%) was injected, the mixture was sealed, and the mixture was shaken in a constant temperature bath at 55° C. for 10 hours. The reaction product was poured into methanol to remove unreacted monomers, washed, and then dried under vacuum to obtain 6.6 g of white powder. The hydroxyl value of the 1q polymer is 0.60 (
glycidol in the polymer (3.2 mol%). In addition, this polymer was dissolved in monochlorobenzene containing 1% by weight of the antioxidant [Tsuklak N5-6J O, to a concentration of 0.1% by weight, and the reduced viscosity of this solution measured at 80°C was 0.50.
Met. Example 2 A catalyst was prepared in the same manner as in Example 1 using 60 g of dibutyl i;t=l=side and 133 g of tributyl bosphate. However, the reaction temperature was 250°C. The carbon content of the catalyst material obtained was 29% by weight. Ternary copolymerization of epichlorohydrin, propylene oxide, and glycidol was carried out using the catalyst 2511I'J. 21- 2.3 g (49.4 mol%) of epichlorohydrin, 1.4 g (47.9 mol%) of propylene oxide, and 0.1 g (2.7 mol%) of glycidol were placed in a sealed tube in the same manner as in Example 1. Polymerization was carried out at 40°C for 20 hours. After the polymerization, unreacted monomers were removed from the reaction mixture under reduced pressure, and after repeated washing with water, it was dried under reduced pressure. 3.4 g (88% yield) of sticky solid polymer were obtained. The hydroxyl number of this product was 2.62, and the reduced viscosity measured in the same manner as in Example 1 was 0.66. Example 3 Into a reaction vessel similar to Example 1, 26.5 g of soot ethyltin oxide and 105 g of dibutyl phosphoric acid were placed, and the temperature was gradually lowered while stirring, and the mixture was heated to 240°C for 6 minutes. The obtained product was treated in the same manner as in Example 1 to obtain a catalyst. After putting 50 m' of the above catalyst into a polymerization test tube and dehumidifying it,
Epichlorohydrin 8.2g -22= (81.8 mol%), allyl glycidyl ether 1.1
g (8.9 mol%), glycidol 0.75 g (
9.3 mol %) and 8 g of hexane were added to 14 people and polymerized. After reaction at 40° C. for 30 hours, 9.3 g of highly viscous polyether was obtained. The hydroxyl value of this product is approximately 2.5
．． The iodine value was approximately 35. Applicant Osaka Soda Co., Ltd. Agent Patent Attorney Toru Mayo 23-

Claims (1)

[Scope of Claims] Compounds represented by the following general formulas (I) to (V), RaSi'X4-a (I) provided that the above (I)
) In the formula, R is an aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms, and these groups may have a substituent containing a hetero atom. Further, when a=2 or more, R may be the same or different. X is a hydrogen atom, a halogen atom, a hydroxy group, or an alkoxy group. It is a group selected from an aryloxy group and an acyloxy group, and when a=2 or 1, X may be the same or different. a is an integer from 1 to 4. (RiS++)cX', (I[) However, in the above formula (I), R' is a group selected from R and ×Y in the formula (I>1 [),
At least one of R' is Rt'. X' is a carbonate group,
A group selected from Group J consisting of a phosphorus oxygen acid group, a polybasic carboxylic acid group, and a polyhydric alcohol residue. C is X'
is a number greater than 1 corresponding to the basicity of . RdS++Oe'<III) However, in the above formula (I[), R is the same as R in formula (■). d is 1 or 2T', and when d=1, e=
372. When d=2, e=1. Further, the compound of formula (III) may form a complex with the compound of formula (I). R' + R231-0) V3+182- R' (
IV) However, in the above formula (IV), R is the same as R in formula (I>), and R' is the same as R' in formula (In). The child is a positive integer. ÷R23TI~l-M L'masu (V)2- However, in the above formula (V), R is the same as R in formula (I), and L or L' is oxygen atom or 0 111 -C-O-, and in the case of -C-O-, M is a group bonded with carbon. 1-Dopi may be the same or different. M is It is a saturated or unsaturated hydrocarbon group. g is a number larger than 1. Group J consisting of: one or more selected organotin compounds (A), and the following general formulas (VI) to (■ ) Compound (tlo)3 P=O(VI) (No) 2 P-0-P (01-1> 211
II (Vll)O0 Z-P(ON)2 (■) 1 However, in the above formula (■), Z is an aromatic group. Glycidol and E-membered ring epoxy, characterized in that a reaction product obtained by mixing and heating one or more complete or partial esters (B) of phosphorous acid complexes selected from the group consisting of glycidol and E-membered ring epoxy is used as a catalyst. J for copolymerization with id:
A new method for producing polyethers.