JPS6012363B2 - Method for producing oxyalkylene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing high molecular weight oxyalkylene polymers.

More specifically, the present invention relates to a method of increasing the molecular weight by reacting an alkylene oxide addition polymer with a polyfunctional halogen compound. The present inventors have already proposed a method for producing an oxyalkylene polymer having a high molecular weight and having an allyl-type olefin group at the end (Tokudo Sho 48-6
4567).

That is, alkylene oxide is used as a starting material, caustic potassium is used in an amount of 3 mo]% to 3 hol% based on the alkylene oxide, and most of the caustic potassium remains heterogeneous in the polymerization system at a polymerization temperature of 20 to 100°C. This is a method for producing an oxyalkylene polymer having an allyl-type olefin group at the terminal, which is characterized in that alkylene oxide is addition-polymerized in a dispersed state, and then reacted with an allyl halogen compound. In the production method proposed by the present inventors, oxyalkylene polymers having an arbitrary molecular weight of 500 to 10,000 are controlled by controlling the polymerization time, polymerization temperature, type of co-catalyst such as alcohol, type of base and alkylene oxide, etc. Although it is possible to obtain an oxyalkylene polymer with a high molecular weight of 4,500 or more, it is questionable from a practical standpoint because it requires a long polymerization time at a very low polymerization temperature. there were.

As a result of continuing various studies on this point, the present inventors discovered that a high molecular weight oxyalkylene polymer can be easily obtained by treating with a polyfunctional halogen compound that terminates polymerization, and has developed the present invention. Reached. The present invention is based on a patent application filed in 1973.
The present invention provides a method for producing a high molecular weight oxyalkylene polymer by reacting an alkylene oxide addition polymer as shown in No. 8-64567 with a polyfunctional halogen compound to increase the molecular weight of the polymer. .

To further explain the present invention in detail, in the method for producing an oxyalkylene polymer having a terminal allyl olefin group, which the present inventors have already proposed, 3 hol% to 3 hol% of caustic potassium is used based on the alkylene oxide. There must be.

If less than 3 hol% of caustic potassium is used, it is difficult to reliably convert the hydroxyl groups of the oxyalkylene polymer having hydroxyl groups at the terminals generated by chain transfer into alkoxide groups, so after polymerization, the polymerization solution is It is impossible to increase the molecular weight efficiently using a polyfunctional halogen compound.

If 3 hol% or more of caustic potassium is used and the polymerization conditions are well adjusted, most of the hydroxyl groups of the oxyalkylene polymer having hydroxyl groups at the terminals generated by chain transfer can be converted into alkoxide groups, and as a result, the final The efficiency of the molecular weight increase reaction can be increased.

The greater the amount of caustic potash, the higher the efficiency of the molecular weight increase reaction, so it is more preferable to use the amount of caustic potash equal to or greater than the shoe ol%. Conventionally, in the production of oxyalkylene polymers having a terminal hydroxyl group, a polymerization temperature of 80 to 16 0, particularly a high polymerization temperature of 100 or more, is used.
This method using a low polymerization temperature has advantages such as suppressing the generation of propenyl groups, and is therefore suitable for producing the oxyalkylene polymer that is the starting material of the present invention. Specific examples of monomer components of the alkylene oxide polymer used in the present invention include ethylene oxide, propylene oxide, isobutylene oxide, and 1-butene oxide, and mixtures of these alkylene oxides may be used, but especially Propylene oxide or a mixture of propylene oxide and other alkylene oxides is most preferred. In the present invention, the molecular weight of such an oxyalkylene polymer is increased by treating it with a polyfunctional halogen compound.

Generally, there are two types of reaction types when an alkoxide group reacts with an organic halogen compound.

These are olefin production reactions through a nucleophilic substitution reaction as shown in formula '1} and an elimination reaction as shown in {21]. In order to increase the molecular weight by causing a polyfunctional halogen compound to act on the alkoxide group at the end of the polymer, it is necessary to carry out a substitution reaction corresponding to formula [11], while a reaction such as formula [2] increases the molecular weight. It is necessary to select a polyfunctional halogen compound that not only does not increase the number of polymers, but also generates hydroxyl groups at the end of the polymer, so that it is necessary to select a compound that does not cause the reaction of the '2} type as much as possible. That is, as a polyfunctional halogen compound, the general formula (in the formula, n
is an integer of 0 to 2, m is an integer of 1 to 4; R2 is an m-valent organic group that is bonded to a group through a carbon atom and does not have a hydrogen atom on the carbon atom: R is an m-valent organic group: Z is -○ -, one S-, and a divalent group selected from: Z is an oxygen atom or a sulfur atom; × is a halogen atom: YI to Y4 are selected from a halogen atom, a hydrogen atom, and a monovalent organic group group, and at least two or more of YI to Y4 are halogen atoms.

) are suitable.

Specific examples of polyfunctional halogen compounds include methylene chloride, chloroform, carbon tetrachloride, methylene bromide, methylene iodide, methylene dihydride, 1,1-dichloro-2,2
-dimethylpropane, penzal chloride, penzal bromide, bis(chloromethyl)benzene, pis(promomethyl)benzene, tris(chloromethyl)benzene, 4,4'-
Bis(chloromethyl)biphenyl, 4,4'-bis(chloromethyl)diphenyl ether, bis(chloromethyl)naphthalene, bis(dichloromethyl)benzene, bis(chloromethyl)ether, bis(chloromethyl)thioether, pis (chloromethyl)ketone, pis(chloromethyl)formal, bis(chloromethoxy)benzene, tris(chloromethoxy)benzene, tetrachlorethylene, trichloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, 1,2-dibromoethylene , phosgene, acid chloride, etc. The amount of the polyfunctional halogen compound to be used can vary depending on the molecular weight of the target polymer or the degree of functionality of the halogen compound, but it is 1/8 to 5 times the number of moles of the polymer. Used in the molar range.

In order to obtain a high molecular weight polymer, the higher the functionality of the halogen compound, the better, and depending on the amount of the halogen compound used, the molecular weight of the produced polymer has a maximum value. That is, if the amount used is too small or too large, the highest molecular weight cannot be obtained, so it is necessary to select the optimum addition ratio for each polyfunctional halogen compound used. A tentative guideline for obtaining the highest molecular weight polymer is 1 for the number of moles of polymer produced at the end of polymerization.
This can be successfully achieved by using a polyfunctional halogen compound in an amount of /N to 2/N times (N' represents the number of halogen atoms contained in the polyfunctional halogen compound). The reaction temperature for reacting the polyfunctional halogen compound is 0°C to 10°C.
A temperature of 000 can optionally be used. Further, the reaction can be sufficiently completed within a reaction time of 1 minute to 3 hours. The reaction reagents used in the present invention, ie, the alkylene oxide polymer, the polyfunctional halogen compound, and the solvent, are preferably dehydrated and dried as much as possible.

The high molecular weight oxyalkylene polymer produced easily and inexpensively in the present invention can be used as a polymer plasticizer as it is, but it can also be used as a raw material for urethane, and after introducing an allyl olefin group at the terminal. By utilizing the reactivity of the allylic olefin group, it can be used as a raw material for various reactions.

For example, a silicon hydride compound having a hydrolyzable functional group on a silicon atom can be reacted with a terminal allyl-type olefin group in the presence of a platinum catalyst to form an oxyalkylene polymer having a silicon functional group at the terminal. As a curable composition, this polymer can be a very useful material as a sealing material, caulking material, waterproofing material, covering material, potting material, paint, adhesive, etc. Examples will be specifically described below, but the present invention is not limited to these examples.

Example 1 A commercially available pellet-like caustic potash was finely ground in nitrogen, and a nitrogen-substituted 200 millimeter containing an electromagnetic fly dressing layer was prepared.
4.5 min (80 mm) in a pressure-resistant glass reaction vessel with a capacity of
ol) Take.

Ethylene glycol 0.07' (1.
2 kite mol), propylene oxide 56.6 (0.
After adding 81 mol) at room temperature, the reaction vessel was sealed.
The mixture is stirred at a speed that allows the caustic potash powder to be uniformly dispersed in the system, and the temperature is raised to a polymerization temperature of 490°C. After polymerizing for 2 q hours, unreacted propylene oxide was removed under reduced pressure.

After purging with nitrogen and lowering the temperature of the reaction vessel to 30°C, 30% of toluene was added under a nitrogen stream to dissolve the polymer well. Next, bis(chloromethyl)ether 0.46 [(6.7
mmol) and react at 40°C for 1 hour. Caustic potash and potassium chloride are removed by filtering the polymer solution thus obtained. When the volatile components are removed from the filtered polymer solution under reduced pressure, a slightly yellowish viscous liquid polymer is obtained in 46 minutes at a yield of 98%. The number average molecular weight of the produced liquid polymer was about 5,600. In addition, after reacting bis(chloromethyl)ether in the above, further allyl chloride 2.9 [
(35 mmol) and reacted at 60°C for 1 hour, the number average molecular weight was about 5700, and the terminal group
ol% were olefin groups.

Examples 2 to 12 Polymerization, reaction, and post-treatment were carried out in exactly the same manner as in Example 1, except that instead of using bis(chloromethyl)ether, various polyfunctional halogen compounds were used to treat the polymerization solution. Ta.

The results are shown in Table 1. Table 1

Claims (1)

[Claims] 1 1/8 to 5 for addition polymer of alkylene oxide
React double the amount (molar ratio) of a polyfunctional halogen compound,
A method for producing a high molecular weight oxyalkylene polymer, which comprises increasing the molecular weight of the polymer.