JPH03163133A - Polycarbonate-urethane macromonomer - Google Patents

Abstract

PURPOSE:To prepare a useful functional polymer material by incorporating a specific structure and thereby incorporating C-C double bonds into the molecule. CONSTITUTION:A polycarbonate of formula I or II (wherein A is a single bond or an oxyalkylene group of -R1O-; R1 is an alkylene group; and n is 3-200) having hydroxyl groups at the molecular ends is reacted with an ethylenically unsatd. isocyanate in a ratio of the NCO groups of the isocyanate to the OH groups of the polycarbonate of 0.5-1.0 at 20-90 deg.C, if necessary, in the presence of a catalyst and a solvent, to give the title macromonomer of formula III or IV (wherein M is a group having a C-C double bond and a carbamoyl group and bound to an O atom adjacent to the C atom of the carbamoyl group; and R is H, OH, alkyl, or aryl).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polycarbonate/urethane macromonomer having a carbon-carbon double bond in the molecule, which is useful as a raw material for various molded products, paints, fibers, etc. .

[Prior art and its problems] In recent years, many attempts have been made to copolymerize various macromonomers with other monomers to produce functional graft copolymers as a means of developing functional polymeric materials.

For example, acrylic acid ester-based, styrene-based, styrene/acrylonitrile-based, and silicone-based macromonomers are commercially available, and materials that take advantage of the characteristics of each base polymer are being investigated.

On the other hand, polycarbonate resin has the characteristics of high mechanical strength, high heat resistance, and good transparency.
It is widely used as an industrial material.

Therefore, the emergence of macromonomers to develop new functional polymer materials that take advantage of the characteristics of polycarbonate resins is awaited.

[Means for Solving the Problems] In view of the current situation, the present inventor has made various studies and has found that:
The following polycarbonate/urethane macromonomers were discovered and the present invention was completed.

That is, the present invention relates to the following general formula [I] or [II]
It is a polycarbonate/urethane macromonomer represented by

In the general formulas [I] and [I[], A is a single bond or the formula -
R'0- (In the formula, Rl is an alkylene group.) represents an alkyleneoxy group, M has a carbon-carbon double bond and a carbamoyl group, and the carbon atoms of the carbamoyl group are adjacent to each other. It represents a functional group bonded to an oxygen atom, R represents a hydrogen atom, a hydroxyl group, an alkyl group, or an aryl group, and n is an integer from 3 to 200.

When A represents an alkyleneoxy group -R,O-, a specific example of the alkylene group R1 is C H s .

Specific examples of the functional group M having a carbon-carbon double bond and a carbamoyl group, in which a carbon atom of the carbamoyl group is bonded to an adjacent oxygen atom, include CH2-C-COOC}I2
CM2NHCO-, is mentioned.

The polycarbonate/urethane macromonomer according to the present invention has the following general formula [III] or [TV]E formula:
A and n represent the same meanings as above. Indicated by J,
It can be obtained by reacting polycarbonate having a hydroxyl group at the end with an isocyanate compound having a carbon-carbon double bond.

The isocyanate compound having a double bond used at this time includes, for example, unsaturated carboxylic acid isocyanate alkyl ester such as methacryloyloxyethyl isocyanate; for example, vinyl isocyanate, α, α-
Alkenyl isocyanates such as dimethyl-m-isopropenylbenzylisocyanate and α,α-dimethyl-p-isopropenylbenzylisocyanate; methacrylic isocyanate, etc., but vinyl isocyanate and methacrylic isocyanate have low compound stability. , methacryloyloxyethyl isocyanate, α., which is inconvenient to handle and has moderate reactivity for industrial use. Preference is given to using α-dimethyl-m-isopropenylbenzyl isocyanate and α,α-dimethyl-p-isopropenylbenzyl isocyanate, especially methacryloyloxyethyl isocyanate.

Commercially available polycarbonates having hydroxyl groups at the ends, represented by the general formulas [ml and IV], can be used, but
It can also be prepared by a known method such as hydrolyzing a commercially available polycarbonate resin. Its number average molecular weight is suitably in the range of 1,000 to 50,000.

Isocyanate compounds having a carbon-carbon double bond are also commercially available or can be synthesized by known methods.

For example, unsaturated carboxylic acid isocyanate alkyl esters such as methacroyloxyisocyanate are disclosed in U.S. Pat.
No. 54-5921, 62-195354, 63-10750, and 83-10751.

Further, regarding the production of α,α-dimethyl-m-isopropenylbenzyl isocyanate or α,α-dimethyl-p-isopropenylbenzyl isocyanate, U.S. Pat. Same No. 4.377,530, Same No. 4.399.073
It is written in the number etc.

Although the reaction between the polycarbonate represented by the general formula [III] or [IV] and the isocyanate compound having a carbon-carbon double bond proceeds without a solvent, it is preferable to use a solvent for handling reasons.

The solvent used at this time is not limited as long as it does not have active hydrogen that reacts with the isocyanate group.
Examples include dichloromethane, dichloroethane, tetrahydrofuran, dioxane, and the like. Alternatively, a polymerizable vinyl monomer to be copolymerized with the macromonomer in a later step may be used as the solvent.

The reaction between the isocyanate compound and the polycarbonate having a hydroxyl group at the end is carried out at a temperature of 20 to 90°C, preferably 40°C.
It is preferable to carry out the reaction at a temperature of -70°C, and it is preferable to use a catalyst in order to advance the reaction smoothly.

As the catalyst, tertiary amines (eg, triethylamine, 1,4-diazabisic[2.2.2]octane, etc.) and organic tin compounds (eg, diptyltin dilaurate, etc.) are used. The amount of catalyst is the O. l
The range is preferably from 3.0% to 3.0%; if it is less than this, the effect is insufficient, and if it is too much, it is uneconomical and may become an impurity that may affect the performance of the polymer material.

The ratio of both reaction components is isocyanate group (N G O)/
The range where hydroxyl group (OH)=0.5 to 1.0 is preferable.

The reaction time varies depending on the reaction temperature and the type of isocyanate compound, but the reaction must be continued until the absorption of NGO (approximately 2270 cm-1) is no longer observed in the IR spectrum. The selectivity of the reaction is extremely high and it proceeds almost quantitatively. The reaction solution after the completion of the reaction can be used as it is for the next reaction, but if desired, the target macromonomer can also be isolated and purified by removing the solvent under reduced pressure.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
This is just to make it easier to understand.
The present invention is not limited in any way by these Examples.

Example 1 A three-sided flask with a capacity of 300 ml equipped with an agitator, a reflux condenser, and a thermometer was prepared with a polycarbonate having a hydroxyl group (general formula [III], where A is a single bond and n (average) is 26.5 Compound, OH value eo.o; DURACARB manufactured by PPG
(Product name)) 100g, methacryloyloxyethyl cyanate 16.6g, 1. 4-Diazabicyclo[2. 2. 2] Pour 0.044 g of octane and 120 ml of dichloromethane and heat in a water bath kept at 55°C.
When the reaction was carried out under reflux for a period of time, no absorption of NGO was observed in the IR spectrum of this reaction solution. The solvent was removed by evaporation from this reaction solution, first under normal pressure and then under reduced pressure using a water aspirator, to obtain 117.3 g of white to slightly yellow crystals of a macromonomer with general formula A as a single bond and nL: 6.5. .

When this crystal was analyzed, it was found that it still contained some dichloromethane as an impurity. Also, the iodine value is 22.
It was 4.

FIG. 1 shows the IR spectrum of this macromonomer.

Example 2 α, instead of methacrylicyloxyethyl cyanate,
The reaction was carried out in the same manner as in Example 1 except that 21.8 g of α-dimethyl-m-isopropenylbenzyl isocyanate was used. NGO on IR spectrum after 10 hours
Since almost no absorption was observed, the reaction was stopped.
The same process as in Example 1 is carried out, and in the general formula [II], M is a single bond, and n? 6.5 macromono 7-124.1g
(still containing some solvent as an impurity) was obtained. The iodine value was 21.3 g.

[Brief explanation of the drawing]

FIG. 1 shows the dichloromethane elution IR spectrum of a macromonomer obtained by the reaction of a polycarbonate having a hydroxyl group at the end (OH value: 60.0, DUL?UCARRB manufactured by PPG) and methacryloyloxyethyl cyanate.

Claims (1)

[Claims] 1) General formula [I] or general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] [In the formula, A is a single bond or the formula -R_1O- (where R_
1 is an alkylene group. ), M represents a functional group having a carbon-carbon double bond and a carbamoyl group, in which the carbon atom of the carbamoyl group is bonded to an adjacent oxygen atom, R is a hydrogen atom, It represents a hydroxyl group, an alkyl group, or an aryl group, and n is an integer of 3 to 200. ] A polycarbonate/urethane macromonomer represented by: 2) The polycarbonate according to claim 1, wherein M is a functional group represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・Urethane macromonomer.