JPH10182815A - Graft polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new resin having improved blendability with other synthetic resins and excellent heat stability, being moldable at a low temperature when used alone or together with another synthetic resin and being applicable to e.g. a resin modifier by using a phenoxy resin as the main chain component and using a saturated or unsaturated fatty acid having the specified number of carbon atoms as each of the side chains. SOLUTION: The phenoxy resin constituting the main chain component is a reactive-alcoholic-hydroxyl-containing linear polymer obtained from the reaction of bisphenol A with epichlorohydrin. The side chain component is a 12 C or higher saturated or unsaturated fatty acid. The obtained graft polymer has a number-average molecular weight of 5,000-200,000 and has a structure represented by formula I wherein R<1> and R<2> are each H or a 4 C or lower alkyl; R<3> is a 11 C or higher saturated or unsaturated aliphatic hydrocarbon group; m and n are the molar fractions; m+n=1; and m is 0.2-0.85). The difference of the exothermic peak temperature from the melt initiation temperature is 50 deg.C or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel graft polymer having a very small temperature difference between an endothermic peak temperature of a resin measured by a differential scanning calorimeter and a melting onset temperature measured by a Koka type flow tester, and a novel graft polymer thereof. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Phenoxy resin is a linear polymer having a reactive alcoholic hydroxyl group obtained from the reaction of bisphenol A and epichlorohydrin, and is known as an excellent thermoplastic resin. Because it is similar to resin, paint, molding, adhesives, etc.
It is one of the useful materials used in a wide range of fields.
The phenoxy resin can also be used in combination with various different materials, for example, a polyfunctional amino resin, an isocyanate, an epoxy resin, or the like, by utilizing the reactivity of the alcoholic hydroxyl group. In contrast to crystalline resins such as nylon, which have the characteristic of rapidly changing from a low-viscosity liquid phase to a solid phase with only a few degrees of temperature change, this phenoxy resin is a non-crystalline resin, It has the characteristic that the viscosity change in the molten state is extremely small with respect to the change, and therefore its excellent thermal stability (can be molded without deteriorating the characteristics even at a high temperature of about 317 ° C.) It is preferably used in the field of injection molding and compression molding.

[0003]

The above-mentioned phenoxy resin used conventionally has excellent thermal stability,
When using it, there is a problem that a high processing temperature of 200 ° C. or more is required, and also resin materials that can be combined with phenoxy resin can be combined only with those limited by the structure and reactivity of phenoxy resin. There was a problem that it was not possible.

[0004] The present invention has been made in view of the above-mentioned problems in the conventional phenoxy resin. That is,
The present invention has been made for the purpose of lowering the processing temperature, which has conventionally been a problem in phenoxy resins having a reactive alcoholic hydroxyl group in the main chain, and to improve the blendability with other synthetic resins. is there. An object of the present invention is to provide an endothermic peak temperature (glass transition temperature: Tg) evaluated by a DSC (differential scanning calorimeter) method and a melting property evaluated by a Koka flow tester.
In particular, it is an object of the present invention to provide a novel graft polymer having a small temperature difference from a melting start temperature and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a phenoxy resin is used for the main chain component and a saturated or unsaturated compound having 12 or more carbon atoms is used for the side chain component. It has been found that the above objects can be achieved by combining with a saturated fatty acid, and the present invention has been completed.

The novel graft polymer of the present invention has a number average molecular weight of 5,000 to 200,0 represented by the following formula (1).
00.

Embedded image (Wherein, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 4 or less carbon atoms, R ³ represents a saturated or unsaturated aliphatic hydrocarbon group having 11 or more carbon atoms, and n and m are Fraction, where m + n = 1 and m is 0.2
Means a number of 〜0.85. The graft polymer of the present invention preferably has a temperature difference between the endothermic peak temperature in the differential scanning calorimeter and the melting start temperature in the Koka flow tester of 50 ° C. or less.

In the method for producing a graft polymer according to the present invention, a linear polymer comprising a structural unit represented by the following formula (2) and a long-chain fatty acid represented by the following formula (3) or a functional derivative thereof are prepared. Condensing.

Embedded image (Wherein, R ¹ and R ² have the same meaning as described above.) R ³ —COOH (3) (wherein, R ³ has the same meaning as described above.)

[0008]

Embodiments of the present invention will be described below in detail. The linear polymer comprising the structural unit represented by the above formula (2), which is a raw material for producing the graft polymer of the present invention, is a phenoxy resin having a reactive alcoholic hydroxyl group, and comprises bisphenol A and It can be easily synthesized by reacting epichlorohydrin. Further, for example, Tg is around 100 ° C., and the melting start temperature by the Koka flow tester is 260
° C and the hydroxyl equivalent is 0.3 g / 100 g of resin.
Around 5 equivalents is trade name: Phenotote YP-50
(Manufactured by Toto Kasei Co., Ltd.). Further, the linear polymer comprising the structural unit represented by the above formula (2) may have, if necessary, a hydroxyl group having a more active functional group, for example,
It may be converted to a lower ester residue or the like.

The above linear polymer has an average degree of polymerization of 2
Those having a molecular weight in the range of 0 to 1500 are preferable, and those having a molecular weight in the range of 5,000 to 200,000 in terms of polystyrene reduced number average are preferable. Number average molecular weight is 5,0
If it is less than 00, the strength of the molded product is lowered, which is not preferable. If it exceeds 200,000, the condensation reaction (grafting reaction) cannot be performed uniformly, and a product having a predetermined property cannot be produced stably. .

In the present invention, the long-chain fatty acid represented by the above formula (3) and the functional derivative thereof to be condensed with the linear polymer have a saturated or unsaturated aliphatic hydrocarbon group bonded to a carboxyl group. It contains 11 or more carbon atoms, preferably 11 to 29 carbon atoms, and examples thereof include the following. That is, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid (α-
And γ-), ricinoleic acid, stearic acid, 12
-Hydroxystearic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid and natural mixtures thereof, tallow fatty acid, tallow hardened fatty acid, palm oil fatty acid,
Palm oil hardened fatty acids, sugar fatty acids, vegetable oil fatty acids, fish hardened fatty acids, soy hardened fatty acids, coal-derived montanic acid, etc.
And their functional derivatives, for example, halides,
And lower alkyl esterified compounds. Further, a long-chain synthetic fatty acid having a molecular weight of up to about 800, for example, a product commercially available from Petrolite under the trade name Unicid can also be used. The above long-chain fatty acids may be used alone, or two or more of them may be used in combination depending on the physical properties.

The condensation reaction between the linear polymer having the structural unit represented by the above formula (2) and the long-chain fatty acid represented by the above formula (3) or a functional derivative thereof is carried out under a nitrogen atmosphere for 15 minutes.
Performed by heating to 0-290 ° C. In that case, any of a melting method and a solution method may be used.
In the case of the solution method, a solvent capable of dissolving the above-mentioned raw materials may be used, and a solvent such as toluene or xylene capable of removing generated water as an azeotropic mixture can be used.

In the above-mentioned condensation reaction, a known catalyst used for an esterification reaction between an alcohol and a carboxylic acid can be used, and at least one catalyst selected from alkali metal acetates and alkaline earth metal acetates can be used. It is preferably carried out in the presence. Specific examples thereof include, but are not limited to, lithium acetate, sodium acetate, potassium acetate, calcium acetate, nickel acetate, cobalt acetate and the like and hydrates thereof.

Further, organic tin compounds typified by cibutyltin oxide, organic titanium compounds typified by titanium tetrapropoxide, organic germanium compounds, and the like, which are commonly used for performing transesterification, can also be used. When an unsaturated fatty acid is used, a side reaction such as an oxidation reaction and a cross-linking reaction may occur. Therefore, it is preferable to add a radical reaction inhibitor and an antioxidant to the reaction system as necessary.

Further, according to the present invention, the difference between the endothermic peak temperature and the melting start temperature can be reduced by controlling the melting start temperature by controlling the grafting ratio of the above graft polymer. However, the control of the grafting rate is
Specifically, the reaction is carried out by adjusting the carboxyl equivalent relative to the hydroxyl equivalent of the phenoxy resin and charging the raw materials, and terminating the reaction when water generated during the reaction becomes 90% or more of a predetermined theoretical amount. be able to. The completion of the reaction can be confirmed by the absence of an endothermic peak at the melting point of the fatty acid used, as measured by a differential scanning calorimeter.

The graft polymer of the present invention produced by the above condensation reaction has a number average molecular weight (Mn) of 5,000.
~ 200,000, preferably 8,000 ~ 150,0
00, more preferably 10,000 to 120,000
And a weight average molecular weight (Mw) of 10,000
４００400,000, especially 20,000２００200,000
Is preferably within the range. Further, the temperature difference between the endothermic peak temperature in the differential scanning calorimeter and the melting start temperature in the Koka flow tester is preferably 50 ° C. or less. Further, the grafting ratio must be 20 mol% to 85 mol%, that is, m in the above formula (1) needs to be in the range of 0.2 to 0.85, and preferably 30 mol% to 80 mol. %, More preferably in the range of 40 mol% to 80 mol%. When the grafting ratio is lower than 20 mol%, there is no effect of lowering the melting start temperature of the graft polymer.
In addition, the upper limit of the grafting ratio needs to be set to 85 mol% because it is necessary to suppress a decrease in Tg of the graft polymer.

[0016]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The molecular weight analysis was performed by the GPC method (column: Shode).
x KF-80M, solvent: tetrahydrofuran), and a calibration curve was prepared using polystyrene standards and evaluated. Physical property evaluation by a differential scanning calorimeter (DSC) was performed using a differential scanning calorimeter DSC-120 manufactured by Seiko Instruments Inc. That is, the temperature increase and rapid cooling at 10 ° C. per minute were repeated twice, and the endothermic start temperature and the endothermic peak temperature were determined from the endothermic curve at the time of the second temperature increase.

The melting onset temperature and the flow softening point were determined using a Koka type flow tester CFT-500 manufactured by Shimadzu Corporation under the following measurement conditions. Here, the melting start temperature refers to a plunger falling start temperature under the following measurement conditions, and the flow softening point refers to a temperature at an intermediate point from the descent start temperature to the descent end temperature. Measurement conditions: Plunger: 1 cm ² Die diameter: 1 mm Die length: 1 mm Load: 20 kgf Preheating temperature: 20 to 80 ° C Preheating time: 300 seconds Heating rate: 6 ° C / min

Example 1 (Synthesis Example of Graft Polymer Using Phenoxy Resin and Stearic Acid) Phenoxy resin [Phenotote YP-50, manufactured by Toto Kasei Co., Ltd. (corresponding to a hydroxyl equivalent of 0.35 equivalent)] 10
0.00 g, 24.89 g of stearic acid and 0.25 g of calcium acetate hydrate are put into a 500 ml round bottom separable flask and subjected to a melting reaction at 250 ° C. under a nitrogen stream until a predetermined amount of by-product water is not generated. Was. After the reaction,
After cooling the reactor to 220 ° C, the melt was removed and
A graft polymer was obtained (graft ratio: 25 mol%).
The amount of by-products and acetic acid collected was 9 times the total theoretical value.
It was 6% by weight. The endothermic onset temperature and endothermic peak temperature of the obtained graft polymer are 74.6 ° C. and 93.degree.
1 ° C. The melting onset temperature was 130.5 ° C, and the flow softening point was 151.7 ° C. The difference between the endothermic peak temperature by DSC and the melting start temperature by the Koka flow tester was 37.4 ° C. The molecular weight measurement results were as follows: number average molecular weight: 15,300, weight average molecular weight: 84,1
00, and the degree of dispersion (Mw / Mn) was 5.49.

Example 2 The amount of stearic acid used in Example 1 was changed from 24.89 g to 7
To 9.64 g, the amount of catalyst used was changed from 0.25 g to 0.79 g.
A graft polymer was obtained in the same manner as in Example 1 except that g was changed to (g: 80 mol%). The endothermic onset temperature of the obtained graft polymer was 70.6 ° C, the endothermic peak temperature was 89.2 ° C, the melting onset temperature was 110.4 ° C, and the flow softening point was 120.3 ° C. The difference between the endothermic peak temperature by DSC and the flow start temperature by the Koka flow tester was 21.2 ° C. The molecular weight measurement results were as follows: number average molecular weight: 22,800, weight average molecular weight: 1
13,200 and the degree of dispersion was 5.55.

Example 3 (Synthesis Example of Graft Polymer Using Phenoxy Resin and Behenic Acid) The amount of stearic acid used in Example 1 was changed from 24.89 g to 47.83 g of behenic acid and the amount of catalyst was changed from 0.25 g. Except having changed to 0.47 g, it carried out similarly to Example 1, and
A graft polymer was obtained (graft ratio: 40 mol%).
The endothermic onset temperature of the obtained graft polymer is 81.4.
° C, endothermic peak temperature is 99.2 ° C, melting start temperature is 14
0.3 ° C. and the flow softening point was 161.0 ° C. DS
The difference between the endothermic peak temperature by C and the flow start temperature by the Koka flow tester was 41.1 ° C. The number average molecular weight is 17,900 and the weight average molecular weight is 98,80.
0 and the degree of dispersion was 5.52.

Example 4 (Synthesis example of graft polymer using phenoxy resin and palmitoleic acid) The stearic acid used in Example 1 was replaced with 24.71 g of palmitoleic acid, and 0.1 g of hydroquinone was added as a polymerization inhibitor. A graft polymer was obtained in the same manner as in Example 1 except that the grafting was performed (grafting ratio: 80 mol%). The endothermic start temperature by DSC of the obtained graft polymer was 66.6 ° C, and the endothermic peak temperature was 71.3 ° C. The melting start temperature was 87.5 ° C, and the flow softening point was 104.3 ° C. The difference between the endothermic peak temperature by DSC and the flow start temperature by Koka type flow tester is
16.2 ° C. The molecular weight measurement results were as follows: number average molecular weight: 21,600, weight average molecular weight: 118,50
0 and the degree of dispersion was 5.49.

Example 5 In addition to the raw materials used in Example 1, toluene 300 m
was added, and the reactor was equipped with a Dean-Stark water quantifier, and reacted under reflux of toluene. After collecting a predetermined amount of water, toluene was distilled off, and the mixture was heated under reduced pressure to remove the solvent. Thereafter, the melt was taken out to obtain a graft polymer. The endothermic onset temperature of the obtained graft polymer is 74.
7 ° C., endothermic peak temperature 93.0 ° C., melting onset temperature 1
It was 30.4 ° C. and the flow softening point was 151.6 ° C., which was different from Example 1 by ± 0.1 ° C., and there was no significant difference from Example 1. The number average molecular weight is 15,3.
00, weight average molecular weight 84,100, dispersity 5.4
9, which was not different from the case of Example 1.

[0023]

The graft polymer of the present invention is a novel resin having an improved blending property with another synthetic resin and excellent in heat stability, and can be used by itself or mixed with another synthetic resin. It can be molded at a low temperature and can be applied as a resin modifier or the like. Further, according to the production method of the present invention, it is possible to reduce the difference between the endothermic peak temperature and the melting start temperature by controlling the grafting ratio, and it is possible to easily produce a graft polymer having good low-temperature moldability. It is possible to manufacture.

Claims (5)

[Claims] 1. A graft polymer represented by the following formula (1) and having a number average molecular weight of 5,000 to 200,000. Embedded image (Wherein, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 4 or less carbon atoms, R ³ represents a saturated or unsaturated aliphatic hydrocarbon group having 11 or more carbon atoms, and n and m are Fraction, where m + n = 1 and m is 0.2
Means a number of 〜0.85. ) 2. The graft polymer according to claim 1, wherein the temperature difference between the endothermic peak temperature in the differential scanning calorimeter and the melting start temperature in the Koka type flow tester is 50 ° C. or less. 3. The method according to claim 1, wherein a linear polymer comprising a structural unit represented by the following formula (2) is condensed with a long-chain fatty acid represented by the following formula (3) or a functional derivative thereof. A method for producing the graft polymer according to the above. Embedded image (Wherein, R ¹ and R ² have the same meaning as described above.) R ³ —COOH (3) (wherein, R ³ has the same meaning as described above.) 4. The method for producing a graft polymer according to claim 3, wherein the condensation reaction is carried out in the presence of at least one catalyst selected from alkali metal acetates and alkaline earth metal acetates. 5. The method for producing a graft polymer according to claim 4, wherein the catalyst is selected from sodium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate and hydrates thereof.