JPH0343296B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing substantially colorless hydroxyl-terminated poly(chloroalkylene ethers).

Hydroxyl-terminated poly(chloroalkylene ethers) and methods of making them are known. These methods often use cationic polymerization methods,
In that case, oxirane monomers such as alkylene oxides, alcohols, and acid catalysts are used to synthesize hydroxyl-functional prepolymers. For example, US Patent 3850856; 3910878; 3910879;
See 3980579.

The products and methods described in these patents are
I know that I am not completely satisfied. For example, it has proven very difficult to control the temperature of polymerization reactions. Furthermore, the products are dark in color and tend to react very slowly with various materials such as isocyanates unless substantial amounts of catalyst are used. It has also been found to become unstable when exposed to sunlight or temperatures above 50°C. It has also been discovered that when these substances are exposed to light or heat, their color becomes darker and their acidity and water content increase. Additionally, the products described in US Pat. No. 3,980,579 adversely affect the catalytic activity of the amine catalysts used in the production of polyurethane foams.

Other methods of making hydroxyl-terminated poly(chloroalkylene) ethers are also known. Specifically, US Pat. No. 3,450,774 teaches a method for preparing polymers having hydroxyl end groups by cleavage of high molecular weight crystalline poly(epihalohydrins) in the presence of certain alkaline compounds. The resulting polymer is crystalline and has a low molecular weight. Moreover, they only partially have hydroxyl functionality. That is, they may have carbonyl and ethynyl end groups instead of hydroxyl end groups.

The applicant's pending application, Japanese Patent Application No. 54-60247, discloses a hydroxyl-terminated poly(chloroalkylene ether) that is optically clear and colorless, i.e., appears to have the same optical clarity as distilled water. has been done. That is, they exhibit a color magnitude (discussed below) of less than about 10. Furthermore, they are stable to the action of heat and light. That is, they are resistant to deterioration due to such conditions. Furthermore, they have excellent chemical reactivity towards isocyanate substances.

Such colorless materials are particularly useful when the color of the final product is important (eg, when the true color of the product is an important criterion). For example, they are useful in the production of cast urethane systems that can be used as coatings and adhesives, and flooring materials. Furthermore, urethanes made using such materials have been found to exhibit improved properties over prior art urethanes. For example, such urethanes exhibit excellent resistance to grease and oil.

The above patent application No. 54-60247 (Japanese Patent Application No. 54-150497)
A method for preparing such amorphous hydroxyl _- terminated poly(chloroalkylene ethers ₎ , disclosed in US Pat. X is boron, phosphorus, arsenic, or antimony) in the presence of a catalytic amount of a binary catalyst system consisting of a specified molar ratio of
It is characterized by polymerizing one or more hydroxyl-containing substances having six hydroxyl groups and one or more chloroalkylene oxides. The presence of this two-component catalyst system is important, and even if the polyvalent tin compound is missing or bis(fluorinated aliphatic sulfonyl)
Even if the alkane or H _n XF _o+n is missing, the desired colorless substance cannot be produced. In other words, the combination of these two components was essential to the structure.

It has now been unexpectedly revealed that the above colorless substance can be produced even by using a two-component catalyst system consisting of a combination of the above specific polyvalent tin compound and HF.

The present invention provides (i) HF and (ii) formula (wherein g is 0 or 1, R ⁹ and R ⁶ are the same or different groups, and are saturated and unsaturated aliphatic and aromatic hydrocarbyl groups having 1 to 10 carbon atoms) R ⁷ is selected from the group consisting of saturated and unsaturated aliphatic and aromatic hydrocarbyl groups having from 1 to 10 carbon atoms, and R ⁸ is a polyvalent tin compound (selected from saturated aliphatic hydrocarbyl groups having 1 to 10 carbon atoms) (provided that the molar ratio of the tin compound to HF is in the range of 1.13:1 to 3:1). one or more hydroxyl-containing organic substances having from 1 to 6 hydroxyl groups, characterized in that the polymerization is carried out at temperatures between 0°C and 110°C in the presence of a catalytic amount of a two-component catalyst system) from one or more chloroalkylene oxides, the formula (In the formula, R ¹ and R ² are each selected from hydrogen and a methyl group, and R ³ and R ⁴ are hydrogen, a lower alkyl group having 1 to 10 carbon atoms, and 1 to 2 carbon atoms, respectively. is selected from lower chloroalkyl groups having 1 to 5 carbon atoms and 1 to 5 chlorine atoms, R ³ and R ⁴
at least one of is the lower chloroalkyl group, R ⁵ is a residue of an organic hydroxyl substance having 1 to 6 hydroxyl groups, b is an integer of 1 to 50, and d is 1 to 6 is an integer of ).

In the present invention, the ratio of tin compound to HF is
Range of 1.13:1 to 3:1, preferably 1.2:1 to
The range is 2:1.

The resulting poly(chloroalkylene ether) is essentially colorless and exhibits a color index of less than 10.

For simplicity, the hydroxyl-terminated poly(chloroalkylene ethers) of the present invention will be referred to hereinafter as polyols. For purposes of this description, the term "polyol" shall include materials having at least one terminal hydroxyl group.

In addition to being substantially colorless, the poly(chloroalkylene)ether polyols of the present invention also include:
It is an amorphous substance. They therefore do not exhibit a single melting point. Furthermore, they can be of low molecular weight (250 MW) or high molecular weight (5000 MW) based on the average hydroxyl functionality of the polyol.

The polyols of the present invention are prepared by combining a hydroxyl-bearing material, an alkylene oxide (at least about 50% by weight of which is a chloroalkylene oxide), and a catalyst system of the present invention and polymerizing the resulting mixture. Ru. Polymerization is at 0℃
It can be carried out at temperatures ranging from ~110°C. Preferably, the polymerization is carried out at a temperature in the range 40°C to 80°C.

Solvents may also be used in the polymerization mixture. They are particularly useful when one or more of the components of the mixture are solids. Suitable solvents are those that dissolve (but are otherwise inert to) the materials in the mixture, such as cyclohexanedimethanol, benzene, toluene, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, etc. is included.

Although the polymerization proceeds smoothly to completion, some unpolymerized chloroalkylene may remain. This material can be prepared from the poly(chloroalkylene ethers) of the invention by, for example, vacuum distillation, warming the polymerization mixture to 80°C, and subjecting the heated mixture to vacuum (0.01 torr) for a short period of time (1-2 hours). can be separated from

Materials with a variety of hydroxyls are useful in the present invention. For example, they include water, liquid and solid organic materials having at least one hydroxyl functionality. The organic material may be monomeric or polymeric, including monohydric and polyhydric alcohols,
Preferably, haloalkanols and polymerized polyols are chosen.

The hydroxyl groups of the organic material may be terminal or pendant (ie, non-terminal) groups. Hydroxyl materials having both terminal and pendant hydroxyl groups can also be used. The molecular weight of the hydroxyl-containing organic material can vary over a rather wide range. For example, it may range from about 10 to about 2500.

Preferably, the hydroxyl-bearing organic material is an aliphatic material having at least one primary or secondary aliphatic hydroxyl group (ie, the hydroxyl group is bonded directly to a non-aromatic carbon atom).
Most preferably, the organic material is an alkane polyol.

Monohydric and polyhydric alkanols useful in the present invention include methanol, ethanol, isopropanol, 2-butanol, 1-octanol, octadecanol, 3-methyl-2-butanol, 5-
Includes propyl-3-hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol and sorbitol .

Monohydric and polyhydric haloalkanols useful in the present invention include 2-chloroethanol, 3-chloropropanol, 2,3-dichloropropanol, 3,4
-dibromo-1,2-butanediol, 2,3-
dibromo-1,4-butanediol, 1,2,
Includes 5,6-tetrabromohexane-3,4-diol.

Useful hydroxyl-containing polymeric materials of the present invention include polyoxyethylenes with molecular weights from about 200 to about 2000 (corresponding to hydroxyl equivalent weights of 10 to 1000 for diols and 70 to 630 for triols); polyoxypropylene glycols and triols; hydroxyl-terminated polyalkadienes; and polytetramethylene glycols of various molecular weights, such as polymeg 650, 1000 and 2000.
Sold by Quaker Oats Co.
Contains glycols from the Polymeg family.

The useful hydroxyl-containing materials listed above are provided by way of example only. Additionally, other hydroxyl-containing materials are also useful as will be apparent from the results described herein.

The exact hydroxyl-bearing material selected for use in the present invention will depend on the desired terminal hydroxyl functionality of the poly(chloroalkylene ether) polyol. It has been found that the polyols of the present invention have the same hydroxyl functionality as the hydroxyl-bearing starting material, and that the hydroxyl functionality is present as terminal hydroxyl groups.
For example, when using monofunctional hydroxyl materials, monohydric polyethers are obtained;
When using difunctional hydroxyl materials, dihydric polyether polyols are obtained, and so on.

A wide variety of chloroalkylene oxides are useful in the present invention. For example, they include epichlorohydrin, 1-chloro-2-methyl-2,3-
Epoxypropane, 1,4-dichloro-2,3-
Includes epoxybutane, and 1-chloro-2,3-dimethyl-2,3-epoxy-butane. More highly chlorinated monoalkylene oxides are also useful in this invention. Representative examples of these materials include 1,1-dichloro-2,3-epoxypropane, 1,1,1-trichloro-2,3-epoxypropane, 1-bromo-1,1-dichloro-
2,3-epoxy-propane, 1,1-dichloro-1-fluoro-2,3-epoxypropane,
1,1-difluoro-1-chloro-2,3-epoxypropane and the like. Still other useful chloroalkylene oxides include 1,1-dichloro-
2-methyl-2,3-epoxypropane, 1,
1,1-trichloro-3,4-epoxybutane,
1,1-dichloro-3,4-epoxybutane,
1,1,1,2,2-pentachloro-3,4-epoxybutane, 1,1,1,4,4-pentachloro-2,3-epoxybutane, 1,1,1,2,
2-mixed pentahalo-2,3-epoxybutane,
1,1,1,2,2-mixed pentahalo-3,4-
Includes epoxybutane and 1,1,1,2,2-pentachloro-2-methyl-2,3-epoxybutane. Tetrachloroepoxybutane, such as 1,1,4,4-tetrachloro-2,3-epoxybutane, 1,1,2,2-tetrachloro-
3,4-epoxybutane and 1,1,1,2-tetrachloro-3,4-epoxybutane can also be used.

Mixtures of any of the foregoing chloroalkylene oxides can be used, as well as mixtures of at least one haloalkylene oxide and up to about 50% by weight of one or more non-halogenated alkylene oxides. Examples of useful non-halogenated alkylene oxides include propylene oxide, 1-hexylene oxide, cyclohexane oxide, styrene oxide, methyl glycidyl ether, and phenyl glycidyl ether.

By adjusting the ratio of alkylene oxide to hydroxyl-bearing material, it is possible to limit the degree of addition and thus the molecular weight of the polyols of the invention. For example, the molar ratio of hydroxyl groups in the alkylene oxide material to the hydroxyl material is
It may range from 1:1 to 1:50, and the molar ratio is preferably from 1:1 to 1:20.

The catalyst system useful in the present invention consists of (i) HF and (ii) a polyvalent tin compound as described above. Even as little as about 0.05 weight percent of the catalyst system, based on the combined weight of the hydroxyl-bearing material and alkylene oxide, is effective in providing the optically clear, substantially colorless polyols of this invention. be.

Polyvalent tin compounds useful in the catalyst systems of the present invention have the formula (wherein R ⁹ , R ⁶ , R ⁷ , R ⁸ and g are each the same as described above). Particular examples of polyvalent tin compounds of this type include diphenyldibutyltin, divinyldibutyltin, diallyldibutyltin, tributyltin fluoride, triphenyltin acetate, dibutyltin oxide, and bis(tributyltin oxide).

As previously mentioned, the polyols of the present invention are optically transparent; they are substantially colorless as indicated by color index (ie, they have a color index of less than about 10). The color index indicates the deviation of the color of a given material from that of distilled water when both are measured at approximately 25°C. Water color and sample color were determined by Hunder-Associates, 9529 Leh Highway, Fairfax, VA.
Hunterlab Model sold by Laboratory
Measured using a D25-4 color difference measuring device. This instrument measures three parameters that characterize the color of a sample. These parameters are (i) the gray component “L” of the sample, (ii) the red-green (+ value indicating redness and − value indicating greenness) component “a” of the sample, and (iii) the sample’s red-green (+ value indicating redness and − value indicating greenness) component “a”. It is a yellow-blue (+ value indicating yellowness and - value indicating blueness) component "b". The color index (ΔE) is calculated using the following formula.

ΔE=√() ² +() ² +() ² (In the formula, ΔL, Δa, and Δb represent the difference in L, a, and b values of distilled water and the sample to be tested, respectively. Distilled water is 25
The color index is 0 at °C.

Color index values less than about 10 represent optically clear, substantially colorless materials.

The following examples further illustrate the invention. In the examples, parts mean parts by weight unless otherwise noted.

Example 1 Poly(chloroalkylene ether) was synthesized according to the present invention. Cyclohexane dimethanol (36g, MW144, 0.25mol) and catalyst system (0.31g
A mixture of 48% aqueous hydrofluoric acid and 0.17 g of diphenyldibutyltin was heated to 60°C to 65°C. Epichlorohydrin (214 g, 2.31 mol) was slowly added to the mixture while maintaining the same temperature. The reaction mixture was stirred for an additional 16 hours. Vacuum distillation gave a colorless, slightly cloudy poly(chloroalkylene ether) according to the invention in 72% yield. The product is hydroxyl equivalent
332, weight average molecular weight of 838 and color index of 1.69. The yield of this chloroalkylene ether is
An improvement to 97.3% can be achieved by using a catalyst system consisting of 0.75g of 48% hydrofluoric acid and 0.5g of diphenyldibutyltin. The product obtained from this reaction has a hydroxyl equivalent weight of 407.

Claims (1)

[Claims] 1 (i) HF and (ii) Formula (wherein g is 0 or 1, R ⁹ and R ⁶ are the same or different groups, and saturated and unsaturated aliphatic and aromatic hydrocarbyl having 1 to 10 carbon atoms) R ⁷ is selected from the group consisting of saturated and unsaturated aliphatic and aromatic hydrocarbyl groups having from 1 to 10 carbon atoms, and R ⁸ is a polyvalent tin compound (selected from saturated aliphatic hydrocarbyl groups having 1 to 10 carbon atoms) (provided that the molar ratio of the tin compound to HF is in the range of 1.13:1 to 3:1). one or more hydroxyl-containing organic substances having from 1 to 6 hydroxyl groups, characterized in that the polymerization is carried out at temperatures between 0°C and 110°C in the presence of a catalytic amount of a two-component catalyst system) from one or more chloroalkylene oxides, the formula (In the formula, R ¹ and R ² are each selected from hydrogen and a methyl group, and R ³ and R ⁴ are hydrogen, a lower alkyl group having 1 to 10 carbon atoms, and 1 to 2 carbon atoms, respectively. carbon atoms and 1 to 5 chlorine atoms, at least one of R ³ and R ⁴ is the lower chloroalkyl group, and R ⁵ is a lower chloroalkyl group having 1 to 6 chlorine atoms. a residue of an organic hydroxyl substance having hydroxyl groups, b is an integer from 1 to 50, and d is an integer from 1 to 6. . 2 The molar ratio of the tin compound:HF is 1.2:1 to 2:
1. The method of claim 1 within the scope of claim 1. 3. The method of claim 1, wherein the poly(chloroalkylene ether) has a color index of less than 10.