JPS62527A - Polyamide copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer excellent in oil resistance, heat resistance, water absorption resistance and chemical resistance, obtained by polymerizing a specified polyamide component with a specified organosiloxane component. CONSTITUTION:A block polyamide copolymer of a number-average MW of 500-50,000 and J-value of 10-600ml/g is obtained by reacting 1-99wt% polyamide component (A) consisting of structural units of formulas I and/or II (wherein n is 5-11, X is a 6-12C alkylene and Y is a 4-10C alkylene) and having an amino or carboxyl group on each terminal with 99-1wt% polyorganosiloxane component (B) of formula III (wherein l is 2-50, m is 1-6, Q is 0 or a bond, R' is H, methyl or phenyl, R is a bivalent organic group and Z is hydroxyl, amino or carboxyl) and, optionally, 0-30wt% third component (C) of formula IV [wherein J is Z and R'' is an alkylene which may be branched, a polyoxy (1-4C) alkylene residue of a number-average MW of 50-3,000 or the like] at 170-270 deg.C for 1-4hr in an inert gas atmosphere in the presence of an esterification catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel polyamide/polysiloxane copolymer.

(Prior Art) 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, so they can be used for primary products such as rubber (silicone rubber), oil, and plastics, as well as for secondary products using them as raw materials. is put into practical use. 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 carrot plastics, the low temperature Research has been conducted to utilize elasticity to create tubes and hoses with high low-temperature impact resistance, and in the field of medical materials, its biochemical stability has been used to create orthopedic materials, prosthetic materials such as dish tubes, and ointment base materials. There are many things that have already been put into practical use.

Furthermore, its usefulness is attracting attention in the field of gas separation membranes from the standpoint of resource and energy conservation. The gas separations covered here include helium purification, rare gas separation, uranium enrichment, oxygen enrichment, nitanol synthesis, separation and purification of recycled gases such as acetic acid bottoms, and oxygen enrichment membranes are already being used in boilers. It has been put into practical use because of its improved fuel efficiency.

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

(1) A method of kneading polysiloxane 1 with other resins is described, for example, in JP-A-58-98749, Plasti
cs Worla p, 70 March, 198
8 etc.

(2) Chemically convert polysiloxane polymer into polynystyl,
A method for producing a Bolock copolymer by combining it with other polymers such as polynythyl, polyurethane, and polycarbonate is described, for example, by y, y; 1° Roff, Ann,
N, Y-Aca, 5Ci-, 146,119 (19
67), W., J., Ward, J., Mom, Sci.
, 1. It is described in USP 3.781,378, etc.

(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 31, 461 (1982).

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

Among the above-mentioned manufacturing methods, the manufacturing method suitable for developing mechanical, electrical, and physical properties depending on the use of the resin is the one described in (2) above from the viewpoint of ease of molecular design. This method is considered to be a method of chemically bonding a siloxane polymer with another polymer to obtain a block copolymer.

On the other hand, polyamide has long been known for its excellent mechanical properties, heat and abrasion resistance, and excellent surface appearance, making it ideal for use in household, industrial appliances and equipment, and electronic industry parts. It has many uses in , auto parts, gears, etc.

However, for applications such as shoe soles, tightening bands, internal backings and flexible poses used in the automotive industry, conventional polyamide balls also require great flexibility.

For this reason, polyamide elastomers synthesized from polyamides, polynytyls, etc. are used for such purposes.

(Problems to be Solved by the Invention) However, such polyamides and polynythyl copolymers significantly deteriorate their physical properties in the moderate low temperature range of 0°C to 140″C.

Furthermore, since a polyether component is used, there is a drawback that oil resistance is poor.

(Means for Solving the Problems) As a result of extensive research, the present inventors have found that mechanical strength, iiffjM abrasion resistance, and gasoline resistance can be improved by bonding polyamide polymers and polysiloxane polymers with ester or 7-polymer bonds. The fact that a novel polyamide/polysiloxane copolymer can be obtained that maintains the excellent properties of polyamide resin such as hardness and lubricant resistance, and also has heat resistance, water absorption resistance, and chemical resistance. This discovery led to the present invention.

(Structure of the Invention) Thus, according to the present invention, the following general formula (I) and/or (■): NE (Cu2) nCo -) -
・（I）SoM仄′MHCOYCO÷ ・・・
-...α) (where n is an integer of 5 to 11, X is 06-1
A polyamide component (4) having a structural unit containing a fullkylene group (2), Y is an alkylene group (04 to 10) and having amino or carboxyl groups at both ends, and the following general formula a[): (wherein, l is An integer of 2 to 50, 1 is an integer of 1 to 6, Q is an oxygen atom or one bond, G is a hydrogen atom, a methyl group or a phenol group, R is a divalent organic group, 2 is a hydroxyl group, an amino group, or A linear polyamide copolymer obtained by polymerizing a polyorganosiloxane component a3) represented by a carboxyl group through an amide bond or an ester bond, and the J-value of the polyamide copolymer is 10 to 60 (1+t /V is provided.

The structural units of the formula (1) and/or (I) in the polyamide component (2) are constructed from various polyamide-forming monomers by the method described below. Here general formula (I)
Configure? As the 7z do-forming monomer, 06-0
There are 12 ω-lactams or 06-012 ω-axonocarboxylic acids, and specific examples of ω-lactams include caprolactam, enantlactam, decalactam, undecanelactam, and dodecalactam (laurolactam). .

Specific examples of ω-7 minocarboxylic acids include 6-7 main thukabronic acid, 8-7 minocapric acid, 10-7 minodecanoic acid, 11-7 minoundecanoic acid, and 12-7i nododecanoic acid.

Further, as the polyamide-forming monomer constituting the general formula a), there is a salt of a diamine of 06 to C12 and a dicarboxylic acid of 06 to 012.

Specific examples of salts of diamines and dicarboxylic acids include 06 to C12 diamines such as hexamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and adipic acid, azelaic acid, sebacic acid, and dodecane diamine.
Salts with 06-C'12 dicarboxylic acids such as acids may be mentioned.

These boria 2d-forming monomers may be used in amounts of 21i or more.

The polyamide component (2) in this invention requires that both ends thereof be 7 groups or carboxyl groups. Such a polyamide component can be obtained by adjusting the terminal ends of a polyamide obtained from the above polyamide-forming monomer. This terminal adjustment is usually carried out by reacting a dicarboxylic acid or diamine in an equivalent amount with respect to a 7-mino group or a carboxyl group, and the dicarboxylic acid or diamine is as shown in the example of the third component (C) described later. A wide variety of dicarboxylic acids and diamines can be used, and for polyamides of general formula (I), the diamines and dicarboxylic acids used to form the polyamide itself can be used, in other words, by reacting either in excess. You can also get it. Preferred polyamide components (4) include:
Typical examples include hexamethylene diamine modified terminal diamine type polyamide, adipic acid modified terminal dicarboxylic acid type polyamide, and dodecanedioic acid modified terminal dicarboxylic acid type polyamide. Examples include acid type polyamide. However, these terminal adjustments can also be carried out simultaneously during copolymerization with the polyorganosiloxane component. At this time, by controlling the amount of dicarboxylic acid or diamine for terminal adjustment, these can act as a molecular weight regulator.

Polyorganosiloxane component represented by the formula (3) used in this invention CB) C) The following formula GID-1,G[D-2,GI
It is divided into three types: D-3.

These three types of components °a3) are appropriately selected and used so that they can be condensed with the polyamide component (3) to form an amide bond or a nityl bond. For example, when a polyamide with amine groups at both ends is used as the polyamide component, formulas (1)-2 with carboxyl ends at both ends are combined (
amide bond), when using a polyamide with carboxyl groups at both ends, a hydroxyl or amine type formula G [
D-1 or 2〇ID-8 are combined (ester or amide bond). This constitutes a linear copolymer of the present invention in which component (4) and component 03) are bonded in substantially equimolar amounts.

R in formula ① is a divalent organic group, an alkylene group which may have a branch, and a polyokine (C+ to 4) having a number average molecular weight of about 50 to 3000, preferably about 50 to 1000.
Alkyleno residues, divalent alicyclic groups or divalent aromatic groups are suitable. As the divalent alicyclic group, a divalent group containing at least an alicyclic hydrocarbon group can be used, and as the divalent aromatic group, a divalent group containing at least an allyl group can be used.

The above alkylene group is a straight chain or branched 02-8
6 is preferred, and examples of the branched alkylene group include the following. Specific examples of polyoxyalkylene residues include +ClI2'C52O-)-CH2CE2- and (optionally substituted). Furthermore, examples include (optionally substituted with a dikyl group) and the like. The divalent aromatic group may optionally have a nityl bond, a sulfonyl bond, a sulfide bond, or a carbonate bond, and the hydrogen atoms in each of the above groups may be optionally substituted with a halogen atom. It's okay.

On the other hand, the fart in formula (1) means a hydrogen atom, a methyl group, or a huniyl group. These are usually the same groups, but in some cases they may be different from each other.

Component a3) represented by the above formula (2) may be used at -1 or more. In particular, those with low molecular weight [in formula (2), β = 2 and 1 = 1
~2 or l=8 and co=1] and high molecular weight ones [l=5 to 50 and m=1 to 6 or l=B~4 and co=
One preferable embodiment is to use 2 to 6 of these in combination. This is because as the organosiloxane moiety increases, the compatibility between component 03) and component (2) tends to deteriorate, and the resulting polyamide copolymer of the present invention tends to have an extremely low J-value. This is because by using component G3), which has a low molecular weight, the compatibility is improved, the J-value is high, and the material becomes elastic. One reason for this is thought to be that the low molecular weight component CB) facilitates free rotation of the main chain of the copolymer. In this case, the molar ratio of the low molecular weight material to the high molecular weight material is suitably 1:99 to 99:1, preferably 10:90 to 90:10.

In addition, such polyorcasiloxane 1ff 1 minute CB)
Compounds available in the art under the names of i, t, diol at both ends, dicarboxylic acid, or diamine type polyorganosiloxane or modified products thereof can be used.

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

(2) First, a method (two-step method) in which a polyamide component is prepared in advance by polymerization, and this is copolymerized with polyorganosiloxane fl-03).

(2) A method (one-step method) in which the aforementioned polyamide-forming monomer capable of forming the polyamide component (2) and the polyorganosiloxane component G) are copolymerized in the presence of a terminal regulator.

The polyamide copolymer obtained by the above-mentioned two-step process has a polyamide part in the form of one large block, and the main boria blocks suitably have a number average molecular weight of 500 to 50,000, preferably 1,000 to 10,000.

On the other hand, the polyamide copolymer obtained by the above-mentioned one-step method has random polyamide portions.

As a specific two-step polymerization method, the polyamide component (
When copolymerizing 5) with a stoichiometrically equivalent amount of the polyorganosiloxane component) in the presence of a conventional esterification catalyst, under a reduced pressure of about 801 mHy or less, preferably 10 + mHp to 15 mtrEy, 20
An example of this method is to proceed with heating KN synthesis by heating at 0 to 270°C, and then proceed with heating polycondensation at 220 to 270°C under a reduced pressure of 1 wIHy, preferably 0 or 1 WIIH9. In addition, when copolymerizing equivalent amounts of component (4) and component 03) through an amide bond, there is no need to use a catalyst, and an inert gas is introduced at a temperature of about 170 to 270° C. under normal pressure. A method of carrying out heating polycondensation under the same conditions as above may be mentioned. On the other hand, the one-step method includes a method in which an equivalent amount of end-adjusting dicarboxylic acid or Schiff base and an equivalent amount of a polyorganosiloxane component are reacted in the same manner as above with respect to the polyamide-forming monomer and the resulting polyamide. .

In addition, as a nistylation catalyst for ester bond,
There are many tin-based catalysts, titanium-based catalysts, lead-based catalysts, etc., such as difurkyltin oxide such as dibutyltin oxide and dioctyltin oxide; dibutyltin urilate, dibutyltin bis(2-nitylhexane) Examples include dialkyltin alkylates such as Noate); tetraalkyl titanates such as tetrabutyl titanate and tetraisopropyl titanate; titanium salts of sinuate such as potash titanium sinuate; lead compounds such as acetic acid.

Among these, it is preferable to use a tin-based catalyst.

The J-value of the polyamide copolymer of this invention is 10 to 600.
, preferably 20-300. This J-value Cwt/
f"J is an index value for evaluating the solution viscosity of a polymer, which indirectly defines the molecular weight of the copolymer of the present invention,
The measurement method is as follows. (peutsche
austrienorm (])go) 16779
Tend:) Test f10.25y exactly 50! The sample is weighed into a volumetric flask and dissolved using a mixed solvent of 1/1 phenol-10-dichlorobenzene at room temperature or under humidification to bring the total volume to 50 ml. Next, using an Ubbelohde viscometer at 25°C, the falling time of only the solvent and the falling time of the solution containing the sample were measured.

The J-value can be calculated using the following formula.

It is.

The copolymers of this invention consist essentially of an equivalent amount of polyamide component (
It consists of a linear polymer obtained by alternately polymerizing the polyorganosiloxane component 03) and the polyorganosiloxane component 03) through amide bonds or ester bonds. However, component (4) and/or component a3) may also be partially replaced by a third component (C) having the same reactivity as these.

As this partial substitute component, the following general formula av): J-go'
-J...-■C In the formula, J is a hydrogen group, a 71 group, or a carboxyl group, and K is an alkylene group that may have a branch group, a divalent alicyclic group, or a divalent alicyclic group. Aromatic group (However, these groups may contain one or more heteroatoms, and hydrogen atoms may be optionally substituted with hafgen atoms) Are suitable. such third component CO)
When used as a substitute component for polyamide component (5), the usage ratio is usually 1 to 70 mol% or less, and when used as a component of polyorganosiloxane component a3), it is 99 mol% or less. Usually, it is suitable to set it as 1-99 mol%. Especially for CB) ingredients 3~
It is preferably 97 mol%, most preferably 10 to 95 mol%. These third components (C) act to adjust the mechanical strength of the resulting copolymer as a resin; It is preferable to use it normally because it plays an important role and makes the polymerization reaction smoother. In addition, the substitution ratio for component a3) is 9
If it exceeds 9 mol%, the properties of component CB) cannot be obtained substantially, and if the substitution ratio is less than 1 mol%, the compatibility with the partner component in the ester reaction or amide formation reaction tends to decrease, and the properties obtained by component CB) are likely to decrease. This is not preferred because the molecular weight of the copolymer tends to decrease and the J-value tends to be less than 10. On the other hand, if the substitution ratio of component CAJ + Tetsuki exceeds 70 mol%, component (2)
If the amount is less than 1 mol %, the molecular weight tends to decrease as described above, which is not preferable. Note that it is also possible to partially replace both component (1) and component CB) with an appropriate third component (C).

Thus, the present invention provides polyamide component (2), polyorganosiloxane component a3), and these components (2) and/or
Or component (0) as a substitute component for G3) or J-value 10 ~ 7J due to polymerization by amide bond or nistyl bond.
A 600πt/f linear polyamide copolymer is also provided.

The above third component (C) can be divided into three types according to its reactive group, as shown in the following formula: % formula %). This-C) Third component (C
) is usually the same as the reactive group of the component (to) or a3) intended to be substituted. Depending on the case, a material having a different reactive group can be used. For example, as a substitute for the diol-type component a3), in addition to the diol-type third component (C), an amino-type third component can be used. Three components (
C) can be used, or a mixture of these can be used.

Incidentally, among these, the third component (C) of the type represented by the formulas Φ')-2 and 3) can be used as an end-adjusting agent for the polyamide component (support) described above.

// in the formula (1) is an optionally branched alkylene group, with a number average molecular weight of about 50-3000, preferably 50-3000.
1000 polyoxy(Ct~4)alkylene residues, divalent alicyclic groups or divalent aromatic groups which may optionally have an ether bond, sulfonyl bond, sulfide bond or carbonate bond (however, each of these groups (The hydrogen atom may be optionally substituted with a halogen atom), and specific examples thereof include the various groups shown for R in formula (1).

Preferred specific examples of the third component (C) represented by the formula Φ Li-1 include C2~ such as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, and L12-dodecanediol. Ca6
aliphatic diols and alicyclic diols such as cyclohexane dimetatool; polyfulkylenes having a number average molecular weight of 50 to 3000 tH or 300 to 3ooo, such as polypropylene glycol, polytetramethylene glycol, poly-2-methylpropylene glycol; There's glycol. Preferred specific examples of the dicarboxylic acid represented by the formula Φ-2 include succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, acelaic acid, dodecanoic acid,
02-036 aliphatic dicarboxylic acids such as 1,4-cyclohecanedicarboxylic acid and di-7-acid, terephthalic acid,
Examples include aromatic dicarboxylic acids such as isophthalic acid.

Preferred specific examples of the diamine represented by Formula 3 include nethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and 7-diabin (oleic acid). , linoleic acid, dimeric aminated products of unsaturated fatty acids such as linoleic acid), 2.2.4-
02-086 aliphatic diamines such as /2,4.4-)-limethylhexanoethylene diane; 1,,8-/
1.4-bis(7-methyl)cyclohexane, His(
Examples include alicyclic diamines such as 4,4-7minocyclohexyl)methane and isophorone diamine, and aromatic diamines such as xylene diamine and diaminodiphninylmethane.

The preferred weight ratio of each component in the copolymer of this invention is 99 to 1 as component (to): G3): (C):
1-99:0-30, and the most preferable weight ratio is 9
9-50-1-50-0-20.

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

Example 1 As component (4), terminal dicarboxylic acid boria id 12 (Mn=4,000'') 4 O of dodecanedioic acid
f! (0.04 mol), 5 mol% both-terminated butanoloxypolydimethylsiloxane as component G3) 0 = 2
．． 1:13.2)! , :lif (0,002 mol) and component (as ■, 95
Mol% of 1,4-butanediol 8.410-088
mol) was placed in 11 cylindrical flasks. 0.02 f of dibutyltin oxide (Bu2Sn○) was added to the flask as a catalyst, heated to 240°C using a metal bath while introducing nitrogen, stirred for 2 hours, and then heated to 270'C.
The temperature was raised to 150°C, the pressure was reduced to about 15°C using a water jet pump, and the mixture was stirred for 1 hour. Further, at 270℃, use a high vacuum pump to reduce the temperature to 0.05℃.
A vacuum of MMHy was applied and stirring continued for 1 hour. When the obtained product was taken out under nitrogen, it was found to be a white and highly viscous polymer.

The physical properties of the obtained polymer were as follows. In addition, Ty<glass transition point) and Tm (melting point) are D S
O (Mettler TA-2000 type or Park
in-Elmer 2.0 type).

IR: 1745 (ester bond between polydimethylsiloxane and third component and polyamide), 1260°11
00-1000 and 800 (characteristic absorption of polydimethylsiloxane) α-1°lH-NMR: 0.1 (absorption of dimethyl group bonded to silyl group of polydimethylsiloxane) ppm.

J-value: 81m1! /f Ty: 9°C Tm: 151°C Also, from the measurement results of torsional vibration, it is found that the second glass transition point also exists at -123°C.

The above IR chart is shown in FIG.

Example 2 Terminal dicarboxylic acid polyamide 12 (
Mn = 1,000 ) 2 Of (=0.02 m
ol), as component CB), 10 mol% of both terminal butanoloxypolydimethylsiloxane (Mw=1,00
5) 2-01F (=0.002 mol) and component (
0), 90 mol% of 1,4-butanediol 1.
Example 1 except that 62F/(=0.018m01) and 0.01y of dibutyltin oxide were used as the catalyst.
Polymerization was carried out using the same polymerization apparatus and conditions.

The physical properties of the obtained polymer are shown below.

Engineering R: 1745 (ester bond between polydimethylsiloxane and third component polyamide), 1265.1100
~1000 and 800 (characteristic absorption of polydimethylsiloxane) crn-1°'H-NMR2O,1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 78 layer i/9 T tick unclear Tm: 153℃ A chart of IR is shown in FIG.

Example 3 Terminal dicarboxylic acid polyamide 12 (
Mn=7,000)20! (=O, OO286mol
), as component a3), double-terminated butanoloxypolydimethylsiloxane (Mw=645) L84 f(
Polymerization was carried out using the same polymerization apparatus and conditions as in Example 1, except that 0.01 g of dibutyltin oxide (=0.00286 mol) and 0.01 g of dibutyltin oxide were used as the catalyst. The J-value of the obtained polymer was 148 m1/f, Ty was unclear, but Tm was 17
The temperature was 8°C.

The resulting chart is shown in FIG. In addition, the mechanical properties of the obtained porous polyamide copolymer were determined according to DIN 53455.
When measured using the measurement method, the tensile elasticity was 1402N/i
The elongation at break was 20%.

Example 4 As component method), terminal-carphonic acid lyamide 12 (M
n=LOOO)2Of (=0.02 mol), component I
As B), 30 mol% of both terminal phthanoloxy polydimethylsiloxane (Mw=645) 3.871(
=0.006 mol) and component (C), 70
1.26 g of mol% 1,4-butanoneol (=0.0
Polymerization was carried out using the same polymerization apparatus and conditions as in Example 1, except that 14 mol) and 0.02 g of dibutyltin oxide were used as the catalyst. J- of the obtained polymer
The value is 111mt/y and Ty is unclear, but Tm is 151°
It was C. The tensile elasticity of this polymer is 245N/
Fig. 4 shows a chart of one hole in which the elongation at break was 78%.

Example 5 As component (2), terminal dicarboxylic acid polyamide 12 (
Mn=4,000)40f(=0.01 mol
), as component a3), 5 mol % of both terminal dodecanoloxy polydimethylsiloxane (MW=2,105
)1.05f (=0.0005mol) and component (C
) and 95 mol% 1,4-butanoneol 0.8
6g (=0.0095 mol) and as a catalyst,
Example 1 except that 003 g of dibutyltin oxide was used.
Polymerization was carried out using the same polymerization apparatus and conditions.

The physical properties of the obtained 1 copolymer are shown below.

IR: 1743 (polydimethylsiloxane, 4-
ester bond between butanediol and polyamide 12),
1275° 1100-1000 (characteristic absorption of polydimethylsiloxane) m-1° IH-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value, 79mt/f Ty: Unclear Tm:
A chart of the above IR at 172°C is shown in FIG.

Example 6 Component (2) was terminal dicarboxylic acid polyamide 12 (Mn
= 1,000) 30f (=0.03 mol), component a
3), 5 mol% of both terminal propylamine polydimethylsiloxane (Mw = 2,345) 3.521 (=
0.0015 mol) and component (C), 95
Mol% of isophoronediamine 4.85F! (=0.02
Polymerization was carried out using the same polymerization apparatus and conditions as in Example 1, except that 85 mol) was used. Note that no catalyst was used.

The physical properties of the obtained t-copolymer are shown below.

IR: 1265.1100-1000 and 805 (characteristic absorption of polydimethylsiloxane) a-1゜'H-NM
R: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: B: 3mt/f Tg: 37-50°C Tm: 145°C Furthermore, from the measurement results of Tonal Vlbrajlon, it was found that the second glass transition point was at -140°C.

The above IR chart is shown in Figure 6 (?-).

Example 7 Terminal diamino polyamide 12 (n
=2,490)24.9f (=0.01mol)
, using polydimethylsiloxane (Δ4.=2341) with propylamine at both ends as component (I3), and reacting it with dodecanedioic acid at both ends to create a compound of the following formula.
5 mol% (Δ4.=2899)145fiI-
(CH2-8NHCO(CH2)1oCOO■ and 95% as component (C)) v% dodecanionic acid 2.19
Polymerization was carried out using the same polymerization apparatus and conditions as in Example 1, except that the polymer was used. Note that no catalyst was used.

The physical properties of the obtained polymer are shown below.

IR: 1260.1100-1000 and 800 (characteristic absorption of polydimethylsiloxane) crn ○I
H-NMR: 0.1 (absorption of dimethyl group bonded to silicate group) PPm.

J-value: 211 me/fil Tp: 80-45°C Tm: 167°C Further, from the measurement results of 'l'orional vibration, it was found that the second glass transition point was -123°CK. Moreover, the tensile elasticity was 48 ON/m+J and the elongation at break was 287%.

A chart of the above IR is shown in FIG.

Example 8 Terminal diamine polyamide 11 (Mn
=2,000) 20p(0,01m01), component (B)
The same compound as in Example 7 (Mw=2
, 899) 5 mol%, 150y and component (Q, 9
One polymerization was carried out using the same polymerization apparatus and conditions as in Example 1, except that 2.19y of dodecanedioic acid of 5 mo/L/% was used. In addition, the catalyst was not used again.

The physical properties of the obtained polymer are shown below.

IR: 1265.1100-1000 and 805 (characteristic absorption of polydimethylsiloxane) att -10'
H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-tL: IB 6 ml/f”?:
Unknown @ 'I'm: 177°C The above IR chart is shown in Figure 8.0 Example 9 As a component (to), adipic acid modified terminal dicarboxylic acid polyamide 6 (Mn = 1,300) 39F (-0, 03
mol ), as component G3), 90 moJ% double-terminated butanoloxy polydimethylsiloxane (Mw = 71
9) 2.16N (=0.003mol) and component (0
) as 10 mol% 1,4-butanediol 2.4
Example 1 except that Bf (=0.027 mol), τ as the 9ζ catalyst, and 0.021 dibutyltin oxide were used.
Polymerization is carried out using the same polymerization equipment and conditions as t:.

The physical properties of the obtained polymer are shown below.

IH-NMR: 0.1 (absorption of dimethyl group bonded to silyl group) ppm.

J-value: 49πt/9 TF: 12-22℃ 'I'
m: 186°C or higher, which indicates that the polymer in 1hi is a copolymer of polyamide 6 and polydimethylsiloxane.

A chart of the above IR is shown in FIG.

Example 10 11iE portion (4), terminal dicarboxylic acid polyamide 6 (Mn=1,000) 30f (=0.03 mol)
, as component 03), 10 mol% of both terminal propylamine polydimethylsiloxane (Mw=2,345) 7
．． 041 (= 0.OO8mol) and component (0)
as, 90-1-l% diaminodiphenylmethane 5
．． 359 <= 0.027 mol) was used.
Polymerization was carried out using the same polymerization apparatus and conditions as in Example 1.

The physical properties of the obtained polymer are shown below.

1u:NΔB:0.1 (absorption of dimethyl group bonded to silyl group) Also, the tensile elasticity was 709 N/- and the elongation at break was 89%.

Example 11 As component (4), terminal dicarboxylic acid boria 12 (
in = 1,000) 20y, as component CB) 35 mol % of both terminal 2-methylpropanoloxy polydimethylsiloxane (Mw = 867) 6.079 and 65
Mol% of 2-methylpropaturoxytetramethyldisiloxane (Mw=310) 4.0 B F and 0.029 of dibutyltin oxide as catalyst were placed in 14 cylindrical flasks. Next, it was heated to 240°C using a metal bath while introducing nitrogen, and after stirring for 2 hours,
Raise the temperature to 70°C and use a water pump to approximately 151ffllllH
The mixture was stirred for 1.5 hours under reduced pressure. Further, while maintaining the temperature at 270°C, create a true chamber of 0.05 mmHg using a high vacuum pump, and
Stirring was continued for an hour. Under nitrogen, take the product obtained.
When filtered, it turned out to be a white, highly viscous polymer.

The physical properties of the obtained polymer are as follows.

IR: 17.45 (absorption based on ester bond between organosiloxane and polyamide), 1260.1100-1
000 and 800 (absorption based on polydimethylsiloxane) o! -'0'H-NMR: 0.1 (absorption of dimethyl group bonded to silyl group of polydimethylsiloxane)
ppm.

J-value: 18 Bmt/9 T9: Unknown [Trr
,: 149°C Example 12 As component (4), 90 mol % of terminal diamine polyamide 12 (MW = 2,440) 21.96F and 100 mol % of terminal dicarboxylic acid polyamide 12 (MW = 1,0
0(1)1(l and component CB) as 10 mol% propylamine polydimethylsiloxane (Mw=2,8
45) Pour 2.359 into a 14 cylindrical flask.

Next, while introducing nitrogen, the mixture was heated and stirred at 200°C for 1 hour, then the temperature was raised to 250°C, and the pressure was reduced using a water jet pump.
After stirring for 0.5 hours, further stirred at 270°C for 0.01 m
M H? The mixture was stirred for 1 hour under the following conditions.

The J-value of the obtained polymer was 226 rrd/9.

Further, Ty was -50°C, T□ was 168°C, tensile elasticity was 614F/mi, and elongation at break was 11%.

Example 13 Classification (terminated dicarboxylic acid polyamide 12 (M
NX・=4000) 209. Both terminal butanoloxy polydimethylsiloxane as component (B) 2.279
and 1,4-butanediol as component (C)2. sy
Also, 0.015" dibutyltin oxide as a catalyst
into a cylindrical flask. Next, stirring was carried out at 250° C. under normal pressure for 2 hours while introducing the dolphins, and then the pressure was reduced to about 20-30 mmHp using a water jet pump and stirred at 250° C. for 1 hour, followed by 0.1-0. The pressure was reduced to 0.01 mm and stirring was continued at 270'C for 2 hours to obtain a copolymer of the present invention. The J-value of this one combination is 215me
/y and Ty was -70°C, T, J171°C.

In addition, in the above examples, the number average molecular weight of the polyamide component was calculated from the concentration of the amino group or carboxyl group in the terminal group by the following method. The polyamide component was dissolved in this, methanol was added to this, and 0.1 M was dissolved at room temperature.
Titrate with KOH/methanol.

(In case of terminal amine group) In the same manner as above, under room temperature, 0. I M HC, l/
Titrate with methanol.

A: 0.1 Titration number (me) of NHCl F: 〃
Factor W: 2 number of samples (A-D) Xo, IXFXlo-3 Terminal carboxyl group [eq/y] = A: 0. I Titration number of N-KOH Cme) B Droplets of O, 1N-KOH in blank 'i Number Crne
)F: 0. Calculation method of factor average molecular weight M of IN-KOH [terminal amino group (eclA)] + C-terminal carboxyl group (e(]/y)] In addition, the polyamide component (A) used in Examples 1 to 13 above, [in polyorganosiloxane component] and the third component (C), formula (I) and/or formula Gl), formula, and correspondence to formula Φ are shown in Table 1.

(The following margins continue on the next page) (Effects of the invention) Compared to conventional polyamides and polyamide elastomers, the polyamide copolymer of the present invention has better mechanical strength and plasticity at low temperatures, better resistance to hydrolysis, because it contains polyorganosiloxane. This product has improved properties such as hardness, heat resistance, oil resistance, chemical resistance, and two-liquid coagulation property.

Furthermore, the polyamide copolymer of the present invention can be used for textiles, films,
Baka 9 is useful not only as a molded product, but also as a functional polymer for separation membranes and hot melt adhesives that can be used not only at room temperature but also at low or high temperatures. It is an extremely useful material as a biopolymer that takes advantage of its inert properties to living organisms.

[Brief explanation of the drawing]

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

Claims (14)

[Claims] (1) The following general formula (I) and/or (II): -[NH(CH_2)_nCO]-... (I
) −[NHXNHCOYCO]−・・・・・・(II) (In the formula, n is an integer of 5 to 11, and X is C_6_ to_1_2
, Y is an alkylene group of C_4_ to_1_0) as a constituent unit, and a polyamide component (A) having an amino group or a carboxyl group at both ends, and a polyamide component (A) having the following general formula (
III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, l is an integer from 2 to 50, m is an integer from 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 hydroxyl group, an amino group or a carboxyl group), and the polyorganosiloxane component (B) is polymerized through an amide bond or an ester bond. A polyamide copolymer comprising a linear polyamide copolymer having a J-value of 10 to 600 ml/g. (2) The polyamide component (A) has a number average molecular weight of 500 to
The polyamide copolymer according to claim 1, comprising 50,000 block-shaped polyamide parts. (3) The polyamide copolymer according to claim 1, wherein the polyamide component (A) comprises random polyamide portions. (4) In the polyamide siloxane component (B), R in the general formula (III) is an optionally branched alkylene group, a polyoxy (C_1
＿～＿4) Alkylene residue, divalent alicyclic group, or divalent aromatic group that may optionally have an ether bond, sulfonyl bond, sulfide bond, or carbonate bond (however, hydrogen atoms in each of these groups may be optionally substituted with a halogen atom), the polyamide copolymer according to claim 1. (5) The constitutional unit of formula (I) in the polyamide component (A) is formed by ring-opening of ω-lactam of C_6 to C_1_2 or condensation of ω-aminocarboxylic acid of C_6 to C_1_2 The polyamide copolymer described in . (6) The structural units of formula (II) in the polyamide component (A) are diamines of C_6_ to_1_2 and C_6_ to_1
The polyamide copolymer according to claim 1, which is formed by condensation of _2 with a dicarboxylic acid. (7) The following general formula (I) and/or (II): -[NH(CH_2)_nCO]-... (I
) −[NHXNHCOYCO]−・・・・・・(II) (In the formula, n is an integer of 5 to 11, and X is C_6_ to_1_2
, Y is an alkylene group of C_4_ to_1_0) as a constituent unit, and a polyamide component (A) having an amino group or a carboxyl group at both ends, and a polyamide component (A) having the following general formula (
III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, l is an integer from 2 to 50, m is an integer from 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, and Z is a hydroxyl group, an amino group or a carboxyl group); and the polyamide component (A) and/or
Or polyorgano, the following general formula (IV) as a partial substitute component for siloxane component (B): J-R''-J... (IV) [wherein J is a hydroxyl group, an amino group or a carboxyl group; R
'' is an alkylene group that may have a branch, a polyoxy(C_1_-_4) alkylene residue with a number average molecular weight of 50 to 3000, a divalent alicyclic group or an ether bond, a sulfonyl bond, a sulfide bond, or a carbonate bond (However, the hydrogen atoms in each of these groups may be optionally substituted with a halogen atom)] with the third component (C) shown as an amide bond. Or a linear polyamide copolymer polymerized by ester bonds, in which the substitution ratio of the polyamide component (A) in the third component (C) is 70 mol% or less, and the polyorganosiloxane component (B) the substitution ratio for is 99 mol% or less, and the J-value of the polyamide copolymer is 10 to
600ml/g polyamide copolymer. (8) The polyamide component (A) has a number average molecular weight of 500 to
The polyamide copolymer according to claim 7, comprising 50,000 block-shaped polyamide chains. (9) The polyamide copolymer according to claim 7, wherein the polyamide component (B) comprises random polyamide chains. (10) In the polyamide siloxane component (B), R in the general formula (III) is an optionally branched alkylene group, a polyoxy(C
_1_ to _4) Alkylene residue, divalent alicyclic group or divalent aromatic group optionally having an ether bond, sulfonyl bond, sulfide bond or carbonate bond (
The polyamide copolymer according to claim 7, wherein the hydrogen atoms in each of these groups may be optionally substituted with a halogen atom. (11) Claim 7 in which the structural unit of formula (I) in the polyamide component (A) is formed by ring-opening of an ω-lactam of C_6_ to_1_2 or condensation of an ω-aminocarboxylic acid of C_6_ to_1_2 The polyamide copolymer described in . (12) The structural units of formula (II) in the polyamide component (B) are diamines of C_6_ to_1_2 and C_6_ to__
The polyamide copolymer according to claim 7, which is formed by condensation of 1_2 with a dicarboxylic acid. (13) The polyamide copolymer according to claim 7, wherein the third component (C) has a substitution ratio of 3 to 97 mol% for the polyorganosiloxane component (B). (14) The polyamide copolymer according to claim 7, wherein the third component (C) has a substitution ratio of 10 to 95 mol% for the polyorganosiloxane component (B).