JP3362437B2 - Block copolymer having a carboxyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention has a carboxyl group
It relates to a block copolymer. [0002] 2. Description of the Related Art Conventionally, thermoplastic resins have been used in various molded products.
It has been used as a material. But a single resin
Alone may not provide sufficient performance, in which case
Is trying to improve the performance by adding other polymer substances.
For example, an aromatic vinyl compound and a conjugated diene compound
Random copolymers, block copolymers and their parts
Thermoplastic resin made by adding a polymer material such as hydride
Compositions are known. However, these polymers
The substance has poor compatibility with the thermoplastic resin, and
The good effect is not enough and the obtained thermoplastic resin
The composition had the disadvantage of poor adhesion. Improved adhesion
With regard to the functionality, a specific functional group is introduced into the polymer
A solution has been developed by giving
(JP-A-62-41213). On the other hand,
As a result of intensive studies by the present inventors regarding the improvement, the aromatic
Block copolymerization of vinyl compound and isobutylene
I found my body to be effective. [0003] In recent years, due to the diversification of use situations of molded articles, etc.
Various performances are required, one of which is low temperature.
There is impact resistance. However, this low temperature impact
With regard to the impact resistance, the above methods have not been sufficiently improved.
Yes, it was not yet satisfactory. [0004] SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies to solve the above drawbacks, carboxy
Novel block copolymers containing
Found to be effective in improving the impact resistance at low temperatures of
The present invention has been completed. [0005] According to the present invention, there is provided:
IfThe following general formula 1And a repeating unit represented byThe following general
Equation 2Having a repeating unit represented by
30,000-500,000, in block copolymer
Has a carboxyl group content of 0.01 to 3% by weight.
A block copolymer is provided. General formula 1: Embedded image (In the formula, x represents 0 or 1.)General formula 2: Embedded image The carboxyl-containing block of the present invention
The copolymer is a novel polymer not described in the literature,The general
A repeating unit represented by Formula 1 and a repeating unit represented by Formula 2
Return unit andHaving. Having such a carboxyl group
The method for producing the block copolymer is not particularly limited.
For example, a block copolymer of styrene and isobutylene
A method for introducing a carboxyl group is exemplified. styrene
And a block copolymer of isobutylene are generally represented by the general formula
An organic compound having a functional group shown in 3 and a Lewis acid
Of styrene and isobutylene in the presence of an initiator system
Can be obtained. [0007]General formula 3: Embedded image (WhereR ¹ Is a hydrogen atom, an alkyl groupOrAryl group
ToR ² Is an alkyl groupOrAn aryl group,R ³ Is halo
Gen atom, alkoxy groupOrShows an acyloxy group. ) The organic compound isGeneral formula 3The functional group shown in
For example, 2-chloro-2-phenyl
Propane, 1,4-bis (2-chloro-2-propyl)
Benzene, 1,3,5-tris (2-chloro-2-pro
Pill) benzene, 2-chloropropane, t-butylchloro
Halogenated compounds such as lido and α-chloroethylbenzene
Compound: 2-methoxy-2-phenylpropane, 1,4-bi
(2-methoxy-2-propyl) benzene, 2,4
6-trimethyl-2,4,6-trimethoxyheptane,
t-butyl methyl ether, isopropyl methyl ether
Compounds having an alkoxy group such as
-2-phenylpropane, 1,4-bis (2-acetoxy
(S-2-propyl) benzene, tris (2-acetoxy)
-2-propyl) benzene, 2,4,6-trimethyl-
2,4,6-triacetoxyheptane, 1,3,5-to
Triphenylmethyl acetate, t-butyl acetate
Any compound having an acyloxy group is used. Yes
The amount of the organic compound used is usually based on 1 mole of isobutylene.
In the range of 0.0001 to 0.002 mol. Metal halides are used as Lewis acids.
For example, BCl₃, BF₃, BF₃OEt₂,
TiCl₄, SnCl₄, AlCl₃Or its chlorine source
Whose mono- or di-substituted with an alkyl group, SbC
l₅, SbF₅, WCl₆, TaCl₅Etc.
You. The amount of Lewis acid used is as described above.Represented by general formula 3Sensuality
It is usually at least equimolar, preferably 1 to 1 mole of the group.
It is in the range of 100 moles. In the polymerization, for example, ammonium salts,
Tylamine, dimethylamine, triethylamine, ani
Amines such as phosphorus and piperidine and ethyl acetate
Such esters can be added. Ammonium
The amounts of salts, amines or esters used are as described above.General formula
Indicated by 3Usually, 0.01 to 1 mol of the functional group.
100 moles, preferably in the range of 0.1 to 10 moles
You. The polymerization can be carried out in the presence of a solvent.
You. The solvent is not particularly limited as long as it is inert to the polymerization reaction.
But not fats such as pentane, hexane, heptane, etc.
Aromatic hydrocarbons; aromatics such as benzene, toluene and xylene
Aromatic hydrocarbons: methyl chloride, methylene chloride, 1,2-dic
Halogenated hydrocarbons such as loroethane, nitromethane,
Nitro compounds such as nitroethane
A mixed solvent and the like can be mentioned. [0012] The polymerization temperature is usually -120 to + 50 ° C,
Preferably it is -100 to + 20 ° C. Especially the polymerization time
Without limitation, types of organic compounds, Lewis acids, amines,
It can be adjusted by the amount used. For example, the polymerization method
For example, from an organic compound having two functional groups and a Lewis acid
Polymerizes isobutylene in the presence of an initiator system
There is a method of performing polymerization by adding styrene into the polymerization system.
It is. The iso-block of the block copolymer thus obtained is
The butylene content and styrene content are between 50 and 9 for isobutylene.
5% by weight, preferably 55-90% by weight, styrene content
It is 5 to 50% by weight, preferably 10 to 45% by weight. The block copolymer of the present invention is, for example,
By introducing a carboxyl group by the method shown below,
Can be obtained. Lithating agent for block copolymer
And after contact with the lithiation accelerator, the electrophilic compound
A method of contacting is exemplified (JP-A-62-41213).
Method described in Japanese Patent Publication No. As the lithiating agent, for example,
Methyl lithium, isopropyl lithium, n-butyl lithium
Titanium, sec-butyllithium, ter-butyllithium
And lithium alkyls such as dodecyllithium
Can be The amount of lithiating agent used is usually
For 1 unit (corresponding to the number of benzene rings), 0.
001 to 3 equivalents. Examples of the lithiation accelerator include N,
N, N ', N'-tetramethylethylenediamine, tet
Laethylethylenediamine, N, N, N ', N'-tetra
Laalkyl-1,2-diamino-cyclohexane, tri
Amines such as ethylenediamine are used. Lichiu
The amount of the accelerator used is usually based on 1 equivalent of the lithiating agent.
From 0.01 to 100 equivalents. As the electrophilic compound, for example, carbon dioxide
Element, ethylene oxide, aldehyde, ketone, carvone
Acids and their salts and esters, aryl halides,
Epoxide, sulfur, isocyanate, sulfonate
Which is used. The amount of electrophilic compound used is usually
It is 1 to 100 equivalents to 1 equivalent of the humidifier. The block copolymer, the lithiating agent and the lithium
Contact with the electrolysis compound and the electrophilic compound
Usually performed at -70 to + 120 ° C for 1 minute to 24 hours
You. In the thus obtained block copolymer,
The content of the ruboxyl group is 0.0% per block copolymer.
1-3% by weight, preferably 0.05-1.5% by weight,
More preferably, the content is 0.07 to 1.0% by weight. Also,
Number average molecular weight (gel permeation chromatography
Polystyrene equivalent value obtained by the-method) is 30,000
~ 500,000, preferably 30,000-30
It is 0000. The block having a carboxyl group of the present invention
By blending the copolymer with the thermoplastic resin,
The impact resistance at a low temperature of the conductive resin can be improved. [0019] The present invention will be described in more detail with reference to the following examples.
Will be described. Note that, in the examples, comparative examples and reference examples,
% And% are by weight unless otherwise specified. Example 1 7.7 liters of methyl chloride and methylcyclohex
4.7 liters of sun, 1,4-bis (2-chloro-2-
Propyl) benzene 5.8 g, triethylamine 2
6.6 grams, 85.4 grams of titanium tetrachloride and iso
Add 1.28 kilogram of butylene, at -70 ° C for 1 hour
After the polymerization, 870 g of styrene was added, and a further 0.3 g was added.
The polymerization reaction was continued for hours. Of the resulting block copolymer
The yield was 100%. Bound styrene content is 33.9
% (Calculated by NMR), number average molecular weight is 76.0
00. Next, under a nitrogen gas atmosphere, cyclohexa
Dissolve 400 grams of block copolymer in 3 liters
And a hexane containing 12.4 grams of sec-butyllithium.
181 ml of a sun solution, N, N, N ', N'-te
Add 47.3 ml of tramethylethylenediamine.
The mixture was reacted at room temperature with stirring. After the viscosity increases,
Tetrahydrofuran 60 containing 5 grams of carbon dioxide
Add 0 ml and stir until the viscosity decreases.
247 ml of an aqueous acid solution was added and further stirred.
Of course, 400 g of a block copolymer having a carboxyl group
Got a ram. Block copolymer having a carboxyl group
of¹H-NMR and IR measurement values are shown below.¹ H-NMR (CDCl_Three) Δ (ppm): 0.8-1.
3, 1.3 to 1.7, 1.7 to 2.1, 6.4 to 6.
8, 6.8-7.3, 7.6-8.0 IR (cm^-1): 2950, 2900, 2850, 17
00,780,700 A block copolymer having a carboxyl group
Dissolve 0.2 g in 100 ml chloroform
Dissolve and titrate 0.02N potassium hydroxide / ethanol
Potentiometric titration with solution and indicator thymolphthalein
And determine the content of carboxyl groups per block copolymer.
It was 0.24% when measured. Embodiment 2 1,4-bis (2-chloro-2-propyl) benzene
Other than using 5.0 grams and 430 grams of styrene
Was polymerized in the same manner as in Example 1, and the bound styrene content was 2
5.3% (calculated by NMR), number average molecular weight 6
5,000 block copolymers were obtained with a yield of 100%.
Next, in a nitrogen gas atmosphere, 3 liters of cyclohexane
Dissolve 400 grams of block copolymer in
Hexane solution 181 containing 12.4 grams of chilled lithium
Milliliter, N, N, N ', N'-tetramethylethyl
Add 47.3 ml of diamine and stir
The reaction was performed at room temperature. After the viscosity increases, carbon dioxide 1
800 millimeters of tetrahydrofuran containing 2.5 grams
Add 1 liter, stir until the viscosity decreases, and add 1N aqueous hydrochloric acid.
After adding 247 ml of the liquid and further stirring,
400 grams of a block copolymer having ruboxyl groups
Obtained. Block copolymer having a carboxyl group
of¹H-NMR and IR measurement values are shown below.¹ H-NMR (CDCl_Three) Δ (ppm): 0.8-1.
3, 1.3 to 1.7, 1.7 to 2.1, 6.4 to 6.
8, 6.8-7.3, 7.6-8.0 IR (cm^-1): 2950, 2900, 2850, 17
00,780,700 Block copolymer having a carboxyl group
Dissolve 0.2 g in 100 ml chloroform
Dissolve and titrate 0.02N potassium hydroxide / ethanol
Potentiometric titration with solution and indicator thymolphthalein
And determine the content of carboxyl groups per block copolymer.
The measured value was 0.60%. Reference Example 1 Polycarbonate (Teflon A220 manufactured by Idemitsu Petrochemical Co., Ltd.)
0, number average molecular weight 28,000) 70 parts and the cal of Example 1
Kneading 30 parts of a block copolymer having a boxyl group,
After pelletization using an extruder, a test piece was prepared. Trial
Measure the Izod impact strength, tensile strength, elongation and hardness of the specimen
Specified. Izod impact strength conforms to JIS K-7110
Determined according to (measuring temperature -30 ° C), 22.9
(Kgf ・ cm ・ cm^-2, With notch). Tension
The strength was determined according to JIS K-7113.
(Dumbbell deformation No. 3, tensile speed 100 mm / min),
456 (kgf · cm^-2)Met. Growth is JIS K
Calculated based on -7113 (Dumbbell deformation 3
No., tensile speed 100 mm / min) and 80%.
When the hardness was determined based on JIS K-7215,
68.8.

Continuation of the front page (56) References JP-A-5-310868 (JP, A) JP-A-5-295054 (JP, A) JP-A-5-295053 (JP, A) JP-A-3-287606 (JP) JP-A-3-287605 (JP, A) JP-A-3-281604 (JP, A) JP-A-3-174403 (JP, A) JP-A-62-141213 (JP, A) 60-20918 (JP, A) WO 93/14135 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 297/00 C08F 8/00

Claims (1)

(57) [Claims] (1)The following general formula 1The repeating unit indicated by
When,The following general formula 2And a repeating unit represented by
When the average molecular weight is 30,000 to 500,000,
The carboxyl group content in the copolymer is 0.01 to 3
% By weight.General formula 1: Embedded image (In the formula, x represents 0 or 1.)General formula 2: Embedded image