JPS6055021A - Production of polyamide/polysiloxane block copolymer - Google Patents

Abstract

PURPOSE:To form the titled copolymer which still retains inherent characteristic properties of a polyamide resin and is excellent in water resistance, water absorption resistance, and chemical resistance, by linking a polyamide polymer with a polysiloxane polymer through a suitable urethane bond. CONSTITUTION:Use is made of at least one polysiloxane (number-average MW of 200-20,000) of formula I , II, or III (wherein M is alkylene, phenylene, or oxyethylene, R is H, methyl or phenyl, n is 0-50, and t, p, and q are each 0-5). Namely, a polyamide (number-average MW of 500-10,000) having a dicarboxylic acid or a diamine on each end, obtained by the polycondensation of a 2-15C lactam (or an alpha,omega-amino acid) or the polycondensation of a 2-15C dicarboxylic acid with a diamine, is linked with the above polysiloxane via a compound having at least two isocyanato groups (e.g., tetramethylene diisocyanate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polyand/boria oxamp copolymer. For more details,
The present invention relates to a method for producing a novel polyamide/polysiloxane block copolymer obtained by bonding a polyamide polymer and a porin 2-loxane polymer through urethane bonds.

In recent years, resins or resin mixtures containing polysiloxane polymers have attracted attention. As is well known, polysiloxane polymers have excellent physicochemical properties such as heat resistance and cold resistance, and are used in primary products such as rubber (silicone rubber), oil, and plastics, as well as in various secondary products using them as raw materials. It is served to. Furthermore, in recent years, research has been conducted in a wide variety of fields to develop various functions of polysiloxane polymers while maintaining the above-mentioned physicochemical properties.

For example, in the field of engineering plastics, research is being conducted to utilize its low-temperature elasticity to create thick tubes and hoses that are resistant to low-temperature impact, and in the field of medical materials, its biochemical stability is used to create orthopedic materials.

Many materials have already been put into practical use as prosthetic materials for blood vessels, ointment base materials, and the like. Furthermore, its usefulness is attracting attention in the field of gas separation membranes from the standpoint of resource and energy conservation. Gas separation and 11. These include helium purification, rare gas separation, uranium enrichment, oxygen enrichment, and ethanol synthesis.

Oxygen enrichment membranes have already been put into practical use for the purpose of improving the fuel efficiency of boilers, such as in the separation and purification of recycled gases such as those used in acetic acid synthesis.

Methods for producing resins or resin mixtures containing polysiloxane polymers include the following.

(1) A method of directly kneading a polysiloxane polymer with other resins is described, for example, in JP-A-58-9S749, Plasti
csWorld p, 70 Maroh+1983%
The contents are listed on .

(2) Chemically convert polysiloxane polymer into polyester,
Methods for producing block copolymers by combining them with other polymers such as polyethers, polyurethanes, and polycarbonates are described, for example, in W, L, Roff, Ann, N, Y
, Aod, Sol,, 146.119N9671゜W, J, Ward, ; J, Morn, Soi,,
1, USP M, 781.378, etc.

5-(3) A method of graft polymerizing polysiloxane to a suitable backbone polymer is described, for example, in JP-A-57-135007, Proceedings of the Society of Polymer Science and Technology 31, 461 (1982).

(4) A method of synthesizing a polymer by anionic polymerization of a polymerizable group containing polysiloxane as a substituent in the side chain is described, for example, in Japanese Patent Publication No. 52-21021.

Among the above-mentioned various manufacturing methods, the manufacturing method suitable for developing mechanical, electrical, and physical properties depending on the use of the resin is the polysiloxane described in (2) above from the viewpoint of ease of molecular design. It is thought that this method involves chemically combining a polymer with another polymer to obtain a block copolymer.

As a result of intensive research, the present inventors have succeeded in improving mechanical strength by bonding a polyamide polymer and a polysiloxane polymer with an appropriate urethane bond.

A new Boria 2D that maintains the excellent properties of polyamide resin such as wear resistance, gasoline resistance, and lubricant resistance, while also adding heat resistance, water absorption resistance, and chemical resistance. The present invention has been developed based on a method for obtaining a polysiloxane block copolymer.

That is, the present invention is a polyamide with a number average molecular weight of 500 to 10,000 represented by the following general formula (1) or a dicarboxylic acid polyamide at both terminals and a number average molecular weight of 500 represented by the general formula (2).
~10,000 diamine polyamide at both ends and a number average molecular weight of 200 to 20,000 represented by the following general formula (3), (4), or (5) and having hydroxyl, amino, or carboxyl groups at both ends. A method for producing a polyamide/polysiloxane block copolymer, which comprises bonding one or two selected polysiloxanes with a polysiloxane using a compound having two isocyanate groups. be.

H2O2Mo(OHz)j-NHOO-(OH+lj+k
OOOH (1) (however, j = integer from 2 to 15, k = 1 to
50 integer)HNmo(OH1-NHoo-(OI(,,
l, -'Fuku NH2 (2) 2 2t (t = integer from 2 to 15, m - integer from 1 to 50) CM is an alkylene group, phenylene group or haoxyethylene group, R is H, OH, or phenyl group , n=θ~50, 1=0~
5) CM and R are the same as formula (3), n = D ~ 50, p = D ~ 5
) (M, R are the same as formula (5), n = 0 ~ 50, q = O ~
5) The dicarboxylic acid polyamide or diamine polyamide having carboxyl groups or amino groups at both ends used in the present invention can be obtained by a known method. Such methods include, for example, polycondensation of lactams, polycondensation of amino acids,
Examples include polycondensation of dicarboxylic acids and diamines, and these polycondensation reactions are carried out in the presence of dicarboxylic acids or organic diamines (these functional groups are preferably located at the ends of the hydrocarbon chain). . These dicarboxylic acids or diamines are combined during the polycondensation reaction to form polymeric boriaodo chain moieties. Furthermore, a dicarboxylic acid group,
A cyazine group can be added to the end of this chain to obtain a, #-dicarboxylic acid polyamide, α, #-cyan ζ polyamide. In addition, these dicarboxylic acids and shea act as 1m11MI moderators.

For this purpose, an excess amount of a than that necessary to obtain a dicarboxylic acid polyamide or diamine polyamide of a predetermined molecular weight is used.
, -monodicarboxylic acids, α,ω-diamines are used. By appropriately selecting this excess ratio, the length of the polymer chain, that is, the average molecular weight of the polyamide can be adjusted.

As a specific method of the production method of the present invention, (1) polyamide is first reacted with a compound having two isocyanate groups, and then polysiloxane is reacted to form a boriaod/
Method for obtaining polysiloxane block copolymer; (2)
There is a method in which polysiloxane is first reacted with a compound having two incyanato groups and then reacted with polyamide to obtain a polyamide/polysiloxane block copolymer. Both methods yield similar polyamide/polysiloxane block copolymers. Therefore, the method (1) above will be explained below as a typical example, but the method (2) can also be implemented in the same way.

The polyamide used in the present invention is a lactam or amino acid whose hydrocarbon chain has 2 to 15 carbon atoms, such as caprolactam, enantlactam, dodecalactam, undecanolactam, dodecanolactam, and 11-aminoundecanoic acid.

12-aminododecanoic acid and the like can be used as a starting material.

The polyamide used in the present invention is also a condensation product of dicarboxylic acid and diamine, such as hexamethylene diamine and adipic acid, azelaic acid, sebacic acid or
．． Nylon 6, which is a condensation product with 12-dodecanedioic acid and a condensation product with nonamethylenediamine and adipic acid.
-6.6-9.6-10.6-12 and 9-6 are also included.

Stone dicarboxylic acids and organic diamines used as chain regulators in polyamide synthesis reactions make it possible to obtain boriazoids represented by the above formula (1) or (2) having carboxyl groups or amino groups at both ends. However, the dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 15 carbon atoms, and the cyanide is preferably an aliphatic dicarboxylic acid having 5 to 14 carbon atoms.
Preferred are aliphatic diamines.

Alicyclic or aromatic dicarboxylic acids, diamines can also be used. These dicarboxylic acids and cyanogens are used in an amount in excess of the amount necessary to obtain a polyand having a desired average molecular weight, according to known calculation methods currently used in the field of polycondensation reactions.

Dicarboxylic acid polyand used in the present invention.

The average molecular weight of diamine polyamide is 500 to 10,00
0, preferably 800 to 5,000.

The diisocyanate compound having an isocyanate group at the chain end used in the present invention may be linear or branched, and is not limited to aliphatic, but may be alicyclic or aromatic. Examples include tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2.4-)lylene diisocyanate, diphenylmethylene diisocyanate, and the like. The average molecular weight of such polymethylene diisocyanate is 50 to 8.000, preferably 100 to 5.000.
It is 000. The above-mentioned diisocyanate compounds can be used in an amount of equimolar to twice the molar amount of the dicarboxylic acid polyamide or diamine polyamide, but since incyanate groups are active toward amine groups (-
(The reaction activity decreases in the order of primary amine group and secondary amine group), and it is desirable to carry out the reaction at a low temperature to avoid side reactions.

Catalyst used in the reaction between polyamide and diisocyanate compound! As 7, tertiary amines and heavy metal derivatives are suitable, such as diazabicyclooctane or its derivative diazabicycloundecene, dibutyltin silaurylate, zinc silaurylate, and lead silaurylate. Such a catalyst is almost necessary when diamine polyamide and a diisocyanate compound are reacted, and the reaction is sufficiently rapid even without a catalyst, but there is no problem in adding it. That is, in the reaction of dicarboxylic acid polyamide or diamine polyamide and diisocyanate compound, the above-mentioned catalyst alone or together with an alkali metal or alkaline earth metal alcoholate is used in a proportion of 0.01 to 2 times the total amount of the reaction mixture: %, preferably 0.03 to 1% by weight.

The above-mentioned formula (
3) 1-polysiloxanes having various functional groups as shown in (4) or (5) are reacted in the presence or absence of the above catalyst.

The average molecular weight of the polysiloxane used here is 200
-20,000, preferably 300-18,000. The proportion of polysiloxane used is 0.95 to 1.0% based on the total amount of diisocyanate polyamide urethane.
0.05 mol is suitable.

Reaction solvents include polar solvents as well as aliphatic or aromatic halogenated solvents, such as N,N-dimethylamide, N,N-dimethylformamide, hexamethylphosphorotriamide, m-cresol, O-dichlorobenzene, It can be produced using chlorobenzene, phenol, etc.

The amount of solvent used can vary over a wide range, and generally ranges from 50% (weight 1') to the total amount of reactants.
95 degrees, preferably 60 to 80 degrees.

The polycondensation reaction to obtain the block copolymer can be carried out simply by heating the reaction mixture at a temperature in the range of 110 to 180°C, preferably 120 to 160°C. When adding the reaction components, each reaction component is added dropwise little by little, and after the reaction is completed, the copolymer is separated from the reaction solvent and purified by a known method to obtain it.

The production reaction according to the invention can advantageously be carried out in two stages. That is, in the first step, either the dicarboxylic acid polyamide at both ends or the diamine polyamide at both ends is reacted with a part or the entire amount of the diisocyanate compound in a solvent, and then in the second step, the diol at both ends and the dicarboxylic acid polyamide at both ends are reacted. A selected one of polysiloxanes having no acid and a diamine at both terminals is introduced into the same solvent to produce a boriaod/polysiloxane block copolymer.

Based on its excellent physical properties, the block copolymer of the present invention has
Hoses, tubes, seals, sealing materials,
Alternatively, it is suitable for use in the production of belt type cicadas such as caterpillars and belts.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A cooling pipe, a dropping funnel, a stirrer, and a nitrogen introduction pipe were attached to a four-eye flask, and the reactor was filled with rollbenze: 150 ttt.
Add 50 rttl to phenol and phenol, and add diamine lauryl lactam oligomer (number average molecular weight Mn = 2300) at both ends while bubbling N2 to 25 tC1.
0.6 mmol), heated to 1 la°C, and then gradually cooled to around room temperature. Dodecamethylene diisocyanate
5.5F (21.7 mmol) was gradually added using a dropping funnel while stirring vigorously. After the dropwise addition was completed in about 5 minutes, stirring was continued for about 30 minutes.

Next, both terminal diol polydimethylsiloxane (Mn=1
700) 18.5 f (10,6 mmo'l) of DBU (diazabicycloundecene) quadruple ft%N,
0.1 m/N-dimethylacetamide solution was added, diluted with 20*l of chlorobenzene, and gradually added dropwise over about 30 minutes at room temperature while stirring using a dropping funnel.

After the addition was completed, the reaction mixture was heated under reflux at 130"C for 1 hour. The reaction mixture was precipitated in methanol, finely ground in methanol using a grinder, and then vacuum dried (
0.1 mgHg) at 80°C for about 3 hours.

The solvent was rectified, then zeolite A-58-12 mesh (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added, and the solvent was sufficiently dried.

Thickness 2 obtained by compression molding the obtained polymer powder sample
The plate III exhibited the following physical properties.

Glass transition temperature [Tg fcl] 1631 Pg crystal temperature [To (℃)'] 5la (Measurement was carried out with a differential thermal analyzer.) Tensile strength at 20℃! 458ky/1s2(
According to JIS K-7111) Elongation at break at 20°C 183% ( ) Example 2 Using the same equipment as in Example 1, 100 m of chlorobenzene and 50 m of tophenol were placed in the reactor, and N2 was bubbled. However, both ends of cyamine lauryl lactam oligomer (Mn-2300) 25f (10.6 mmol
) was added, heated to 130°C, and then slowly cooled to around room temperature. Dodecamethylene diisocyaner) 5.48 f
(21.7 mmol) was gradually added to the reactor using a dropping funnel while vigorously stirring the inside of the reactor. After the dropwise addition was completed in about 15-5 minutes, stirring was continued for about 30 minutes. Next, both terminal carbinol polydimethylsiloxane (λ(n
-2400) 26. Of (10.9 mmol) was diluted with 50 rJ of chlorobenzene and gradually added dropwise over 1 hour without a catalyst. Further, after the dropwise addition was completed, heating and refluxing was performed at 130° C. for 1 hour. The reaction mixture was precipitated in methanol, pulverized in methanol, and then dried in a vacuum dryer (0.1 mmHg) at 80°C for about 3 hours.

A plate with a thickness of 2 mm obtained by compression molding the obtained powder sample exhibited the following physical property values.

Tg('C): 165 Ta(℃l: 1052
Tensile strength at 0°C: 522 ky/6n22
Elongation at break at 0°C: 300% Applicant's agent Kaoru Furuya = 16- Te 3 sales Neho-t, IE Accommodation: (Sponsored) F/Polysilo 1~・Production method of block copolymer 3 Relationship with the case of the person making the amendment Patent applicant Daicel Hierus Co., Ltd. Ne1 4 Agent Nakai Building, 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo Claims and Detailed Description of the Invention Column 6 of the Specification Contents of Amendment (1) Amend if the statement of the claims is attached to a separate sheet -
,,-,,/, \ +1.1 Specification page 6 lines 4-8 "The following general formula...
...or (5)" was corrected as follows [lactam or α with a hydrocarbon chain of 2 to 15 carbon atoms]
, obtained by polycondensation of ω-amino acids, or polycondensation of dicarboxylic acids and diamines having a hydrocarbon chain of 2 to 15 carbon atoms,
and a dicarboxylic acid polyamide at both ends or a diamine polyamide at both ends with a number average molecular weight of 500 to 10,000, whose both ends are carboxyl groups or amino groups, and the following general formula +
11. +21 or (3)" (1) Delete the description from the bottom 4th line to the last line on page 6 of the same page (r (3) of formula (3) on page 7 of the same page)
1J is corrected as r fil J (1) r of formula (4) on page 7 (4) J is corrected as r +21 J (11 r of formula (5) on page 7 of same) (5) J is r (31J and correction (1)
1 in the line next to formula (4) and the line next to formula (5) on page 7
"Same as formula (3)" is corrected to "same as formula (1)" (1,) "This method...
...Correct "these" to "1, that is, the above" +11 Same as 9
Page 11-12 lines “amino acid” is replaced with “α.

ω-amino acid-I and correction (page 10 between 1 and 1, line 7 "'" - notation..." is deleted) (11 page 12, 3 lines from the bottom "2 (31, +41 or (5)
)” to [Formula (11, (21 or (3))” 2. Claim number average molecular weight displayed on Himataniwa plate 200 to 20.00
A polyamide/ A method for producing a polysiloxane block copolymer. -RR 111 110-Mt-5i-0-(Sin) n-3i-n-
3i-(11111 RR (M is an alkylene group, phenylene group or oxyethylene group, R is T(, CH, or phenyl group, n is 0 to 50,
t is 0 to 5) 11 RR (M and R are the same as Nikawa, n is O to 50, p is O to 5) fil RR (M and R are the same as the substitute, n is 0 to 50, q is 0 ~5)

Claims (1)

[Claims] A number average molecular weight of 500 to 500 expressed by the following general formula (1)
10.000 dicarboxylic acid polyamide at both ends or a number average molecular weight expressed by general formula (2) 500 to 10.00
00 both terminal diamine boria Z and the following general formula (!S)
, number average molecular weight 20 expressed in (4) or (5)
0 to 20,000 and one or more polysiloxanes selected from polysiloxanes having a hydroxyl group, an amino group, or a carboxyl group at both ends with a compound having two isocyanate groups. A method for producing a polyamide/polysiloxane block copolymer as mold. HOOOMo [OH21:, MHOOI OH21j%
0OOH (1) (where j is an integer from 2 to 15, k is from 1 to
50 integer) H2N -E-c 01(,,),7NH
OO-tou21. %NH2(2) (however, tJd:
an integer of 2 to 15, m is an integer of 1 to 50) (M is an alkylene group, phenylene group or oxyethylene group, P is) I
, 011. or a phenyl group, n is 0 to 50. t is 0~
5) (M and R are the same as formula (5), n is ~50, p is 0~
5) (M and R are the same as formula (3), n is 0 to 50, q is 0 to
5)