JPH0635509B2 - Polyamide copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polyamide / polysiloxane copolymer.

(Prior Art) In recent years, attention has been paid to a resin or a resin mixture containing a polysiloxane polymer. As is well known, since polysiloxane polymers have excellent physicochemical properties such as heat resistance and cold resistance, they are used as primary products for rubber (silicone rubber), oil, varnish, etc. The product is put to practical use. Further, in recent years, research has been conducted in various fields in order to bring out various functions of polysiloxane polymers while maintaining the above physicochemical properties. For example, in the field of engineering plastics, research has been conducted to make tubes and hoses that have high low-temperature impact resistance by utilizing their low-temperature elasticity, and in the field of medical materials, orthopedic materials utilizing their biochemical stability, Many have already been put to practical use as prosthetic materials for blood vessels, ointment base materials and the like. Further, its usefulness is drawing attention in the field of gas separation membranes from the viewpoint of resource saving and energy saving.
As the target gas separation here, helium purification,
Noble gas separation, uranium enrichment, oxygen enrichment, ethanol synthesis,
For example, separation and purification of recycled gas for acetic acid synthesis, etc., and oxygen-enriched membranes have already been put to practical use because they improve the fuel efficiency of boilers.

The method for producing a resin or resin mixture containing a polysiloxane polymer is as follows.

(1) A method of directly kneading a polysiloxane polymer with another resin is disclosed in, for example, JP-A-58-93749, Plastics World.
p.70 March, 1983, etc.

(2) Polysiloxane polymer chemically polyester,
A method for producing a block copolymer by combining with another polymer such as polyether, polyurethane or polycarbonate is described in, for example, WLRoff, Ann.NYAcd, Sci. , 146 , 1
19 (1967), WJWard, J.Mom.Sci., 1, USP 3,781,378 and the like.

(3) A method of graft-polymerizing polysiloxane on a suitable trunk polymer is described, for example, in JP-A-57-135007, Proceedings of the Polymer Society of Japan 31 , 461 (1982).

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

Among the various production methods described above, the production method suitable for expressing mechanical, electrical, and physical properties depending on the use of the resin is the polysiloxane of (2) above from the viewpoint of ease of molecular design. It is considered to be a method of chemically combining a polymer with another polymer to obtain a block copolymer.

On the other hand, polyamide has long been known to have excellent mechanical properties, heat resistance and wear resistance, and an excellent surface appearance, and is used for household and industrial appliances and devices, electronic industrial parts. , Has many uses in automobile parts, gears, etc.

However, for applications such as shoe soles, tightening bands, internal packing and flexible hoses used in the automobile industry, greater flexibility is required than conventional polyamides.

Therefore, a polyamide elastomer synthesized from polyamide and polyether is used for such an application.

(Problems to be Solved by the Invention) However, such a polyamide or polyether copolymer has a low temperature range of 0 ° C. to −40 ° C.
Its physical properties are significantly reduced.

Further, since the polyether component is used, there is a drawback that the oil resistance is deteriorated.

(Means for Solving the Problems) As a result of earnest research by the present inventors, mechanical strength, abrasion resistance, and gasoline resistance were improved by forming an ester or amide bond between a polyamide polymer and a polysiloxane polymer. We found the fact that a new polyamide / polysiloxane copolymer can be obtained that retains the excellent properties of polyamide resin such as heat resistance, lubricating oil resistance, etc., and also imparts heat resistance, water absorption resistance, and chemical resistance to it. The present invention has been achieved.

(Structure of the Invention) Thus, according to the present invention, the following general formula (I) and / or
(II): (In the formula, n is an integer of 5 to 11, X is a C _{6 to} C ₁₂ alkylene group, and Y is a C _{4 to} C ₁₀ alkylene group) as a structural unit, and both terminals are amino groups or carboxyl groups. Polyamide component (A) and the following general formula (III): [In the formula, 1 is an integer of 2 to 50, m is an integer of 1 to 6, Q is an oxygen atom or one bond, R'is a hydrogen atom, a methyl group or a phenyl group, R is a divalent organic group, Z is a linear polyamide copolymer obtained by polymerizing the polyorganosiloxane component (B) represented by a hydroxyl group, an amino group or a carboxyl group) by an amide bond or an ester bond. A polyamide copolymer having a value of 10 to 600 ml / g is provided.

The constituent units of the formula (I) and / or (II) in the polyamide component (A) are composed of various polyamide-forming monomers by the method described below. Examples of the polyamide-forming monomers constituting general formula (I), a ω- amino acids ω- lactams or C ₆ -C ₁₂ in C ₆ -C _12, specific examples of particularly ω- lactam Include caprolactam, enantolactam, decalactam, undecanelactam and dodecalactam (laurolactam). Specific examples of ω-aminocarboxylic acid include 6-aminocaproic acid, 8-aminocapric acid, 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

As the polyamide-forming monomers constituting general formula (II), there are salts of dicarboxylic acids of diamines and C ₆ -C ₁₂ in C ₆ -C _12.

Specific examples of salts of diamines and dicarboxylic acids include C _{6 to} C ₁₂ diamines such as hexamethylenediamine, undecamethylenediamine, and dodecamethylenediamine, and adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Such salts with C _{6 to} C ₁₂ dicarboxylic acids are mentioned.

Two or more kinds of these polyamide-forming monomers may be used.

The polyamide component (A) in the present invention needs to have amino groups or carboxyl groups at both ends. Such a polyamide component is obtained by adjusting the terminal of the polyamide obtained from the above-mentioned polyamide-forming monomer. This terminal adjustment may be usually carried out by reacting an equivalent amount of dicarboxylic acid or diamine with respect to an amino group or a carboxyl group. The dicarboxylic acid or diamine of the general formula (I
The polyamide consisting of I) can be obtained by using the diamine or dicarboxylic acid used for forming itself, in other words, by reacting either of them in excess. Preferred polyamide component (A), include those dicarboxylic acids and diamines ends adjustment of C ₆ -C _12, and representative examples thereof include hexamethylenediamine transformer terminal diamine type polyamide, adipic acid-modified-terminated dicarboxylic acid type Examples thereof include polyamides and dodecane diacid modified terminal dicarboxylic acid type polyamides. However, these terminal adjustments can also be performed at the same time as the copolymerization with the polyorganosiloxane component (B). At this time, by controlling the amount of the dicarboxylic acid or diamine for terminal adjustment, these can act as a molecular weight modifier.

The polyorganosiloxane component (B) represented by the formula (III) used in the present invention has the following formula (III) -1, (III) -2, (III)
-3 can be divided into three types.

These three types of component (B) are appropriately selected and used so that they can be condensed with the polyamide component (A) to be used to form an amide bond or an ester bond. For example, polyamide component
When both end amino group polyamide is used as (A), both end carboxyl type formula (III) -2 is combined (amide bond), and when both end carboxyl group polyamide is used, both end hydroxyl groups are combined. Or the amino type formula (I
II) -1 or formula (III) -3 are combined (ester or amide bond). This constitutes the linear copolymer of the present invention in which the component (A) and the component (B) are bound in substantially equimolar amounts.

Wherein R in (III) is a divalent organic group, an alkylene group which may have a branched extent a number average molecular weight 50 to 3000 preferably about 50 to 1000 polyoxy (C ₁ ~ ₄₎ alkylene residue Groups, divalent alicyclic groups or divalent aromatic groups are suitable. A divalent group containing at least an alicyclic hydrocarbon group can be applied as the divalent alicyclic group, and a divalent group containing at least an allyl group can be applied as the divalent aromatic group.

As the alkylene group, a linear or branched C _{2 to} C ₃₆
Is preferred, and examples of the branched alkylene group include Etc. Specific examples of the polyoxyalkylene residue include: Or Etc.

Specific examples of the divalent alicyclic group include: (Optionally substituted with a lower alkyl group) and the like. Further, specific examples of the divalent aromatic group include: (Optionally substituted with a lower alkyl group) and the like. The divalent aromatic group may have an ether bond, a sulfonyl bond, a sulfide bond or a carbonate bond, and as a specific example thereof, Etc.

The hydrogen atom in each of the above groups may be optionally substituted with a halogen atom.

On the other hand, R'in the formula (III) means a hydrogen atom, a methyl group or a phenyl group. These are usually the same groups,
Depending on the case, they may be different from each other.

One or more kinds of the component (B) represented by the above formula (III) may be used. Especially low molecular weight [in the formula (III), l = 2 and m = 1 to 2 or l = 3 and m = 1] and high molecular weight [l = 5 to 50 and m = 1. .About.6 or 1 = 3 to 4 and m = 2 to 6] is a preferable embodiment. The reason for this is that when the amount of the organosiloxane moiety increases, the compatibility between the component (B) and the component (A) becomes poor, and the J-value of the obtained polyamide copolymer of the present invention tends to be extremely low. This is because by using the component (B) having a low molecular weight of the siloxane moiety in combination, the compatibility is improved, the J-value is high, and the elasticity is increased. One reason for this is considered to be that the low molecular weight component (B) facilitates free rotation of the main chain of the copolymer. In this case, it is suitable that the molar ratio of low molecular weight to high molecular weight is 1:99 to 99: 1.
10:90 to 90:10 is preferable.

As the polyorganosiloxane component (B), a compound that is available in the art under the name of both-end diol, dicarboxylic acid or diamine type polyorganosiloxane or a modified product thereof can be used.

There are the following two methods for polymerizing the polyamide copolymer of the present invention.

First, a method in which the polyamide component (A) is prepared by polymerization in advance and is copolymerized with the polyorganosiloxane component (B) (two-step method).

A method (one-step method) of copolymerizing the above-mentioned polyamide-forming monomer capable of forming the polyamide component (A) and the polyorganosiloxane component (B) in the presence of a terminal modifier.

The polyamide copolymer obtained by the two-step method has a block-shaped polyamide portion, and the polyamide block having a number average molecular weight of 500 to 50,000 is suitable, and 1,000 to 10,000 is preferable.
On the other hand, the polyamide copolymer obtained by the one-step method has a random polyamide portion.

As a concrete two-step polymerization method, a polyamide component is used.
(A) is a stoichiometrically equivalent polyorganosiloxane component
In the case of copolymerizing with (B) through an ester bond, in the presence of a usual esterification catalyst, at a temperature of about 170 to 270 ° C. under atmospheric pressure and under an inert gas introduction condition, about 1 to 4 hours ( Reaction under reduced pressure for 1 to 6 hours), and then 200 to 27 under reduced pressure of 30 mmHg or less, preferably 10 mmHg to 15 mmHg.
Heat polycondensation by heating at 0 ° C and further under reduced pressure of 1 mmHg or less, preferably 0.1 mmHg or less, 220 to 270 ° C.
The method of advancing heat polycondensation can be mentioned. Further, when copolymerizing equivalent amounts of the component (A) and the component (B) through an amide bond, it is not necessary to use a catalyst, and the amount is about 170 to 2
There may be mentioned a method of performing heat polycondensation under the conditions of introducing an inert gas at a temperature of 70 ° C. under normal pressure in the same manner as above. On the other hand, in the one-step method, a method of reacting the polyamide-forming monomer and the polyamide obtained thereby with an equivalent amount of the terminal-adjusting dicarboxylic acid or diamine and an equivalent amount of the polyorganosiloxane component in the same manner as described above can be mentioned.

As an esterification catalyst for ester bond,
Suitable are tin-based catalysts, titanium-based catalysts, lead-based catalysts, and the like, for example, dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide; dibutyltin laurate, dibutyltin bis (2-ethylhexanoate), etc. Examples include dialkyltin alkylate; tetraalkyl titanates such as tetrabutyl titanate and tetraisopropyl titanate; titanium oxalate salts such as potassium oxalate; and lead compounds such as lead acetate.
Of these, it is preferable to use a tin-based catalyst.

The polyamide copolymer of this invention has a J-value of 10 to 60.
It is 0, preferably 20 to 300. This J-value [[ml
/ G] is an index value for evaluating the solution viscosity of the polymer and indirectly defines the molecular weight of the copolymer of the present invention.
The measuring method is as follows. 〔Deutsche Industr
ienorm (DIN) 16779 Teil2] 0.25 g of a sample is accurately weighed in a 50 ml measuring flask, and the sample is dissolved by using a mixed solvent of phenol / o-dichlorobenzene 1/1 at room temperature or by heating, and the total volume is dissolved. 50
ml. Next, at 25 ° C., the drop time of the solvent alone and the drop time of the solution in which the sample is dissolved are measured with an Ubbelohde viscometer. The J-value can be calculated by the following calculation.

Note that Is.

The copolymer of the present invention is basically equivalent to the polyamide component.
It comprises a linear polymer in which (A) and the polyorganosiloxane component (B) are polymerized alternately by an amide bond or an ester bond. However, component (A) and / or component (B) may be partially replaced by a third component (C) which has the same reactivity as these. As the partial substitute component, the following general formula (IV): JR ″ -J (IV) [wherein, J is a hydroxyl group, an amino group or a carboxyl group,
R ″ represents an alkylene group which may have a branch, a divalent alicyclic group or a divalent aromatic group (provided that these groups may contain one or more heteroatoms. Well, the hydrogen atom may be optionally substituted with a halogen atom)]] is suitable. The ratio of the third component (C) used is used as a substitute component of the polyamide component (A). In this case, 70 mol% or less is usually 1 to 70 mol%, and when it is used as a substitute component of the polyorganosiloxane component (B), it is suitable to be 99 mol% or less, usually 1 to 99 mol%. The component (B) is preferably 3 to 97 mol%, and most preferably 10 to 95 mol% .The third component (C) is a resin as a resin of the resulting copolymer. It acts as an adjustment of the dynamic strength, but with the above-mentioned component (A) and component (B) From the viewpoint of playing an important role as a compatibilizing agent for these components during the polymerization reaction and further facilitating the polymerization reaction, it is usually preferable to use the above. If the substitution ratio of the component (B) exceeds 99 mol%. component
When the property according to (B) is not substantially obtained and the substitution ratio is less than 1 mol%, the compatibility with the partner component of the ester reaction or amide formation reaction is likely to decrease, and the molecular weight of the resulting copolymer is It is not preferable because it tends to decrease and the J-value tends to be less than 10. On the other hand, the substitution ratio for component (A) is 70 mol%
When it exceeds, the characteristics due to the component (A) are not substantially obtained,
If it is less than 1 mol%, the molecular weight is likely to decrease as described above, which is not preferable. Incidentally, both the component (A) and the component (B) can be partially replaced with an appropriate third component (C).

Thus, the present invention provides a polyamide component (A), a polyorganosiloxane component (B), and these components (A) and / or (B).
The present invention also provides a linear polyamide copolymer having a J-value of 10 to 600 ml / g, which is obtained by polymerizing the component (C) as an alternative component of the above with an amide bond or an ester bond.

The third component (C) the following formula by the reaction group: OH-R "-OH (IV ) -1 HOOC-R" -COOH (IV) -2 H 2 N-R "-NH 2 (IV) - It is divided into three types of 3. These third components (C) are
Usually the same as the reactive group of the component (A) or (B) intended to be substituted is used. However, in some cases, it is possible to use those having different reactive groups. For example, as a substitute component of the diol type component (B), a diol type third component (C) is used.
Other than the diamine-type third component (C) can be used,
Further, these may be mixed and used.

Of these, the third component (C) of the type represented by the formulas (IV) -2 and (IV) -3 can be used as the terminal regulator of the above-mentioned polyamide component (A).

R ″ in the formula (IV) is an alkylene group which may have a branch, a number average molecular weight of about 50 to 3000, preferably 50 to
1000 polyoxy (C ₁ ~ ₄₎ alkylene residue, a divalent alicyclic group or an ether bond, a sulfonyl bond, sulfides bond or carbonate bond to optionally have it may divalent aromatic group (provided that these The hydrogen atom in each group may be optionally substituted with a halogen atom), and specific examples thereof include various groups shown for R in the formula (III).

Specific preferred examples of the third component (C) represented by formula (IV) -1 include ethylene glycol, propylene glycol,
1,4-butylene glycol, 1,3-butylene glycol,
C _{2 to} C ₃₆ aliphatic diols such as 1,12-dodecanediol, alicyclic diols such as cyclohexanedimethanol, polypropylene glycol, polytetramethylene glycol, poly-2-methylpropylene glycol and the like, number average molecular weight 50 to 3000 preferably 300 to 30
There are 00 polyalkylene glycols. In addition, formula (IV)-
Specific preferred examples of the dicarboxylic acid represented by 2 include:
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acid or terephthalic acid C ₂ -C _36, such as a dimer acid, isophthalic acid Aromatic dicarboxylic acids such as Further, as preferable specific examples of the diamine represented by the formula (IV) -3, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, undecanemethylenediamine, dodecamethylenediamine, dimerdiamine (oleic acid, linoleic acid, Dimer amination products of unsaturated fatty acids such as linolenic acid), C ₂ -C ₃₆ aliphatic diamines such as 2,2,4- / 2,4,4-trimethylhexamethylenediamine; 1,3- / 1,4-bis (aminomethyl) cyclohexane, bis (4,4-aminocyclohexyl) methane, alicyclic diamines such as isophoronediamine, and aromatic diamines such as xylenediamine and diaminodiphenylmethane. .

The preferred weight ratio of each component in the copolymer of the present invention is 99-1: 1 to 99: 0 as the components (A) :( B) :( C).
30 and the most preferable weight ratio is 99-50: 1-
It is 5: 0 to 20.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 40 g (0.04 mol) of dodecanedioic acid modified terminal dicarboxylic acid polyamide 12 (n = 1,000) as component (A)
5 mol% of both-end butanoloxypolydimethylsiloxane (Mw = 2,132) 4.3 g (0.002 mol) as (B) and 95 mol% as component (C) as an alternative component of component (B)
3.4 g (0.038 mol) of 1,4-butanediol was placed in a cylindrical flask. 0.02 g of dibutyltin oxide (Bu ₂ SnO) was added to the flask as a catalyst, heated to 240 ° C. using a metal bath while introducing nitrogen, stirred for 2 hours, heated to 270 ° C., and then pumped with a water pump. The pressure was reduced to 15 mmHg and the mixture was stirred for 1 hour. Furthermore, while maintaining the temperature at 270 ° C., a vacuum of 0.05 mmHg was made with a high vacuum pump, and stirring was continued for 1 hour. When the obtained product was taken out under nitrogen, it was a white and highly viscous polymer.

The physical properties of the obtained polymer were as follows. The Tg (glass transition point) and Tm (melting point) are measured by DSC (Mett).
ler TA-2000 type or Parkin-Elmer 2C type).

IR: 1745 (polydimethylsiloxane and ester bond between third component and polyamide), 1260, 1100
˜1000 and 800 (characteristic absorption of polydimethylsiloxane) cm ⁻¹ . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group of polydimethylsiloxane) ppm.

J-value: 81 ml / g Tg: 9 ° C Tm: 151 ° C Also, from the measurement result of Torsional vibration, -123
It was found that there was a second glass transition point even at ° C.

The IR chart is shown in FIG.

Example 2 As the component (A), a terminal dicarboxylic acid polyamide 12 (n =
1,000) 20 g (= 0.02 mol), as component (B), 10 mol% of both-end butanoloxypolydimethylsiloxane (Mw = 1,005) 2.01 g (= 0.002 mol) and as component (C), 90 mol% of 1 1,4-butanediol 1.62g (= 0.018
mol) and the same polymerization apparatus and conditions as in Example 1 except that 0.01 g of dibutyltin oxide was used as the catalyst.

The physical properties of the obtained polymer are shown below.

IR: 1745 (polydimethylsiloxane and ester bond between third component and polyamide), 1265, 1100
˜1000 and 800 (characteristic absorption of polydimethylsiloxane) cm ⁻¹ . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 78 ml / g Tg: unclear Tm: 153 ° C. The above IR chart is shown in FIG.

Example 3 As component (A), terminal dicarboxylic acid polyamide 12 (n =
7,000) 20 g (= 0.00286 mol), butanoloxypolydimethylsiloxane with both ends as component (B) (Mw = 64)
5) Polymerization was carried out in the same polymerization apparatus and conditions as in Example 1 except that 1.84 g (= 0.00286 mol) and 0.01 g of dibutyltin oxide were used as a catalyst. J of the obtained polymer
-Value is 148 ml / g, Tg is unclear, but _Tm is 178 ° C.
It was.

The IR chart obtained is shown in FIG. Further, the mechanical properties of the obtained polyamide copolymer were measured by the measuring method according to DIN53455. As a result, the tensile elasticity was 1402 N / mm ² and the elongation at break was 20%.

Example 4 As the component (A), a terminal dicarboxylic acid polyamide 12 (n =
1,000) 20 g (= 0.02 mol), as component (B), 30 mol% of both-end butanoloxypolydimethylsiloxane (Mw = 645) 3.87 g (= 0.006 mol) and as component (C), 70 mol% of 1 1,4-butanediol 1.26 g (= 0.014
mol) and 0.02 g of dibutyltin oxide were used as the catalyst, and the polymerization was carried out under the same polymerization apparatus and conditions as in Example 1. The J-value of the obtained polymer was 111 ml /
Although the Tg was unclear in g, the Tm was 151 ° C. The tensile elasticity of this polymer is 245 N / mm ² and the elongation at break is 78.
It was in%.

The IR chart obtained is shown in FIG.

Example 5 As the component (A), a terminal dicarboxylic acid polyamide 12 (n =
4,000) 40 g (= 0.01 mol), 5 mol% of both-end dodecanoloxypolydimethylsiloxane (Mw = 2,105) 1.05 g (= 0.0005 mol) as component (B) and 95 mol% of component (C) 0.86 g of 1,4-butanediol (= 0.009
Polymerization was carried out in the same polymerization apparatus and conditions as in Example 1 except that 5 mol) and 0.03 g of dibutyltin oxide were used as the catalyst.

The physical properties of the obtained polymer are shown below.

IR: 1743 (ester bond between polydimethylsiloxane and 1,4-butanediol and polyamide 12), 12
75, 1100-1000 (characteristic absorption of polydimethylsiloxane) cm ^-1 . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 79 ml / g Tg: unclear T _m : 172 ° C. The above IR chart is shown in FIG.

Example 6 As the component (A), a terminal dicarboxylic acid polyamide 12 (n =
1,000) 30 g (= 0.03 mol), 5 mol% of both ends propylamine polydimethylsiloxane (Mw) as component (B)
= 2,345) 3.52 g (= 0.0015 mol) and component (C),
95 mol% isophorone diamine 4.85 g (= 0.0285mo
Polymerization was carried out in the same polymerization apparatus and conditions as in Example 1 except that l) was used. The catalyst was not used.

The physical properties of the obtained polymer are shown below.

IR: 1265, 1100 to 1000 and 805 (characteristic absorption of polydimethylsiloxane) cm ^-1 . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 83 ml / g Tg: 37 to 50 ° C. Tm: 145 ° C. Also, from the measurement result of Torsional vibration, −140
It was found that there was a second glass transition point at ° C.

The IR chart is shown in FIG.

Example 7 As the component (A), a terminal diaminopolyamide 12 (n = 2,49)
0) 24.9 g (= 0.01 mol), both ends propylamine polydimethylsiloxane (M _w = 2341) as component (B)
Was used, and 5 mol% of a compound of the following formula (M _w = 2899) in which dodecanedioic acid was reacted at both ends thereof 1.45 g -(CH ₂ ) ₃ NHOC (CH ₂ ) ₁₀ COOH and 95 as the component (C)
Example 1 except 2.19 g of mol% dodecanedioic acid was used.
Polymerization was carried out under the same polymerization equipment and conditions. The catalyst was not used.

The physical properties of the obtained polymer are shown below.

IR: 1260, 1100 to 1000 and 800 (characteristic absorption of polydimethylsiloxane) cm ^-1 . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 211 ml / g Tg: 30 to 45 ° C. T _m : 167 ° C. Further, from the measurement result of Torsional vibration, −123
It was found that there was a second glass transition point at ° C. The tensile elasticity was 480 N / mm ² and the elongation at break was 287%.

The IR chart is shown in FIG.

Example 8 As component (A), terminal diaminopolyamide 11 (n = 2,000)
0) 20 g (= 0.01 mol), propylaminepolydimethylsiloxane (M _w = 2,345) at both ends used as the component (B), and dodecanedioic acid was reacted at both ends to obtain the same compound (M) as in Example 7. _w = 2,899) 5 mol%, 1.50 g and as component (C) 95 mol% dodecanedioic acid 2.19 g were used,
Polymerization was carried out under the same polymerization apparatus and conditions as in Example 1.
The catalyst was not used.

The physical properties of the obtained polymer are shown below.

IR: 1265, 1100 to 1000 and 805 (characteristic absorption of polydimethylsiloxane) cm ^-1 . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 136 ml / g Tg: unclear T _m : 177 ° C. The above IR chart is shown in FIG.

Example 9 As component (A), 39 g (= 0.03 mol) of adipic acid modified terminal dicarboxylic acid polyamide 6 (n = 1,300), component
As (B), 2.16 g (= 0.003mo) of 90 mol% of both-end butanoloxypolydimethylsiloxane (Mw = 719)
l) and the same polymerization apparatus as in Example 1 except that 2.43 g (= 0.027 mol) of 10-mol% 1,4-butanediol was used as the component (C) and 0.02 g of dibutyltin oxide was used as the catalyst. Polymerization was performed under the conditions.

The physical properties of the obtained polymer are shown below. ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 49 ml / g Tg: 12-22 _Tm : 186
From the above temperature, it is recognized that the above-mentioned polymer is a copolymer of polyamide 6 and polydimethylsiloxane.

The IR chart is shown in FIG.

Example 10 As the component (A), a terminal dicarboxylic acid polyamide 6 (n =
1,000) 30 g (= 0.03 mol), as component (B), 10 mol% of both-terminal propylamine polydimethylsiloxane (Mw = 2,345) 7.04 g (= 0.03 mol) and as component (C), 90 mol% of diamino Diphenylmethane 5.35g (=
Polymerization was carried out in the same polymerization apparatus and conditions as in Example 1 except that 0.027 mol) was used.

The physical properties of the obtained polymer are shown below. ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 68 ml / g Tg: 57 to 65 ° C. T _m : unclear Further, the tensile elasticity is 709 N / mm ² and the elongation at break is 39%.
It was.

Example 11 As component (A), a terminal dicarboxylic acid polyamide 12 (n =
1,000) 20 g, 35 mol% of both ends 2 as component (B)
-6.07 g of methylpropanoloxypolydimethylsiloxane (Mw = 867) and 65% of 2-methylpropanoloxytetramethyldisiloxane (Mw = 310) 4.
03g and 0.02g of dibutyltin oxide as a catalyst
In a cylindrical flask. Then, while introducing nitrogen, the mixture was heated to 240 ° C. using a metal bath, stirred for 2 hours, heated to 270 ° C., depressurized to about 15 mmHg with a water pump and stirred for 1.5 hours. Furthermore, while maintaining the temperature at 270 ° C., a vacuum of 0.05 mmHg was made with a high vacuum pump, and stirring was continued for 2 hours. When the obtained product was taken out under nitrogen, it was a white and highly viscous polymer.

The physical properties of the obtained polymer were as follows.

IR: 1745 (absorption based on ester bond between organosiloxane and polyamide), 1260, 1100-1
000 and 800 (absorption based on polydimethylsiloxane) cm ^-1 . ¹ H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group of polydimethylsiloxane) ppm.

J-value: 188 ml / g Tg: unclear T _m : 149 ° C. Example 12 As component (A), 90 mol% of terminal diamine polyamide 12 (Mw = 2,440) 21.96 g and 100 mol% of terminal dicarboxylic acid polyamide. 10 g of 12 (Mw = 1,000) and 2.35 g of 10 mol% propylamine polydimethylsiloxane (Mw = 2,345) as the component (B) were placed in one cylindrical flask. Then, while introducing nitrogen, 200
After heating and stirring at ℃ for 1 hour, the temperature was raised to 250 ℃, depressurized with a water pump, and after stirring for 0.5 hour, at 270 ℃, 0.0
The mixture was stirred under a high vacuum of 1 mmHg or less for 1 hour.

The J-value of the obtained polymer was 226 ml / g. Also Tg
Of -50 ° C, T _m of 168 ° C, tensile elasticity of 614 N / mm ² and elongation at break of 11%.

Example 13 As component (A), terminal dicarboxylic acid polyamide 12 (Mw = 4
00) 20 g, butanoloxypolydimethylsiloxane at both ends as component (B) 2.27 g, 1,4-butanediol 2.5 g as component (C), and dibutyltin oxide 0.01 g as a catalyst were placed in a cylindrical flask. . Then, while introducing nitrogen, the mixture was stirred at 250 ° C. under normal pressure for 2 hours, then depressurized to about 20 to 30 mmHg with a water pump and stirred for 1 hour at 250 ° C., and depressurized to 0.1 to 0.01 mmHg with a high vacuum pump. Stirring was continued for 2 hours at 270 ° C. to obtain the copolymer of the present invention. This polymer has a J-value of 215 ml / g and a Tg of -7.
The temperature was 0 ° C and the T _m was 171 ° C.

In the above examples, the number average molecular weight of the polyamide component was calculated by the following method from the concentration of amino group or carboxyl group of the terminal group.

(In case of terminal carboxyl group) Benzyl alcohol is heated to dissolve the polyamide component in this, and methanol is added to this, and 0.1M K is added at room temperature.
Titrate with OH / methanol.

(For terminal amino group) In the same manner as above, titrate with 0.1M HCl / methanol at room temperature (calculation method) A: 0.1N HCl drop constant (ml) F: 〃 factor W: g of sample A: 0.1 N-KOH titration constant (ml) B: 0.1 N-KOH titration constant (ml) in blank F: 0.1 N-KOH factor Calculation method of average molecular weight The polyamide component used in Examples 1 to 13 above
(A), polyorganosiloxane component (B) and third component (C)
Correspondence to the formula (I) / or the formula (II), the formula (III) and the formula (IV) in Table 1 is shown in Table 1.

(Effects of the Invention) Compared with conventional polyamides and polyamide elastomers, the polyamide copolymer of the present invention contains polyorganosiloxane and therefore has low mechanical strength, plasticity, hydrolysis resistance, heat resistance, oil resistance and resistance It has improved chemical properties and blood coagulation properties.

Further, the polyamide copolymer of the present invention is a fiber, a film,
Not only is it useful as a molded article, but also as a functional polymer such as a separation membrane or hot melt adhesive that can be used not only at room temperature but also at low or high temperatures. It is an extremely useful substance as a biopolymer utilizing its active properties.

[Brief description of drawings]

1 to 12 are graphs showing IR charts of the polyamide copolymers obtained in Examples 1 to 12 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08G 81/00 NUU 8416-4J

Claims (5)

[Claims] 1. The following general formula (I) or (II): (Wherein, n is an integer of 5 to 11, X is a C _{6 to} C ₁₂ alkylene group, and Y is a C _{4 to} C ₁₀ alkylene group) as a constitutional unit, a terminal dicarboxylic acid polyamide component (A), and General formula (III): [In the formula, 1 is an integer of 2 to 50, m is an integer of 1 to 6, Q is an oxygen atom, R'is a hydrogen atom, a methyl group or a phenyl group,
R is an alkylene group which may have a branch, a polyoxy (C ₁ -C ₄ ) alkylene residue having a number average molecular weight of 50 to 3000, a divalent alicyclic group, or an ether bond, a sulfonyl bond, or a sulfide bond. Or a divalent aromatic group optionally having a carbonate bond (provided that each of these groups has a hydrogen atom optionally substituted with a halogen atom), and Z is a hydroxyl group]. The component (B) is a linear polyamide copolymer obtained by polymerization through an ester bond, and the J-value of the polyamide copolymer is 10 to 600.
A polyamide copolymer which is ml / g and in which the weight ratio of the terminal dicarboxylic acid polyamide component (A) and the polyorganosiloxane component (B) in the polyamide copolymer is 99 to 1: 1 to 99. 2. The polyamide component (A) has a number average molecular weight of 50.
The polyamide copolymer according to claim 1, which comprises block-shaped polyamide moieties of -50000. 3. The polyamide copolymer according to claim 1, wherein the polyamide component (A) comprises a random polyamide portion. 4. A polyamide unit (A) wherein the structural unit of formula (I) is a C ₆ -C ₁₂ ω-lactam ring-opening or a C ₆ -C ₁₂ ω-
The polyamide copolymer according to claim 1, which is constituted by condensation of aminocarboxylic acid. 5. The constitutional unit of the formula (II) in the polyamide component (A) is constituted by condensation of a C ₆ -C ₁₂ diamine and a C ₆ -C ₁₂ dicarboxylic acid. The polyamide copolymer described.