GB2169912A - Polyamide/polysiloxane copolymers - Google Patents

Abstract

There is disclosed a polyamide-polysiloxane copolymer. The polyamide constituent has repeating units of formulae (I) and/or (II): <IMAGE> wherein n is an integer from 5 to 11, X is a C6 - C12 alkylene radical and Y is a C4 - C10 alkylene radical, and has amino groups or carboxyl groups at both terminals. The polyorganosiloxane constituent has the formula (III): <IMAGE> wherein I is an integer from 2 to 50, m is an integer from 1 to 6, Q is an oxygen atom or a direct bond, R' is a hydrogen atom, a methyl group or a phenyl group, R is a divalent organic radical and Z is a hydroxyl group an amino group or a carboxyl group. The constituents are polymerized by amide linkages or ester linkages to give a straight chain copolymer having a J-value of 10-600 ml/g.

Description

SPECIFICATION Polyamide-polysiloxane copolymers The present invention relates to novel polyamidel polysiloxane copolymers.

Recently, resins or resinous mixtures containing a polysiloxane polymer have attracted interest. is generally known that polysiloxane polymers have excellent physi co-chemical properties such as good resistance to heat and anti-freezing property and are put to practical use as rubbers (silicone rubbers), oils and varnishes, and as various secondary products prepared therefrom. Investigations are now being carried out in many technical fields for increasing the uses of polysiloxane polymers while maintaining the above physico-chemical properties. For example, in the field of engineering plastics, investigations have been carried out to prepare tubes and hoses having a high shock resistance at lowtemperatures utilizing the elasticity at low temperatures of polysiloxane polymers.In the field of medical supplies, many polysiloxane polymers have been already putto practical use as orthopedic materials, repair materials for blood vessels, and ointment bases utiiizing their biochemical stability. Polysiloxane polymers are also used in the field of gas-separating membranes, for such purposes as separation, purification and the like of recycling gases in the purification of helium, separation of rare gases, concentration of uranium, enrichment of oxygen, synthesis of ethanol and synthesis of acetic acid. A membrane forthe enrichment of oxygen is already used to give a improved fuel efficiency in boilers.

Processes forthe preparation of resins or resinous mixtures containing a polysiloxane polymer include: (1) A process of kneading a polysiloxane polymer direct with another resin is described, for example, in Japanese Patent Laid-open No. Sho 58-93749, "Plastics World" page 70, March 1983, etc.

(2) Aprocessforthe preparation of a blockcopolymer by chemically bonding a polysiloxane polymer with another polymer such as polyester, polyether, polyurethane, polycarbonate or thelike is described, for example, in Ann. N.Y. Acd. Sci., 146,119(1967) by W.L.Roff,J.Mom,Sci.,1,byW.J.Ward,USP 3,781,378.

(3) A process of graft-copolymerizing a polysiloxane with a suitable trunk polymer is described, for example, in Japanese Patent Laid-open No. Sho 57-135007 and Collected Manuscripts for High Molecular Society 461(1982).

(4) A process for synthesizing high molecules by anionic polymerization of a polymerizing radical containing a polysiloxane as substituent on the side chain is described, for example, in Japanese Patent Publication No. Sho 52-21021.

It is considered that the most suitable process for making resins or resinous mixtures having useful mechanical, electrical and physical properties is process (2) wherein a block copolymer is obtained by chemically bonding a polysiloxane polymer with another polymer.

Polyamides are known to have excellent mechanical properties, heat resistance and abrasion resistance, as well as excellent surface appearance. They are widely used for domestic or industrial instruments and apparatus, electronic parts, automobile parts, toothed wheels and the like.

For uses such as soles of shoes, binding belts, inner packing and flexible hoses for automobiles, however, a higherflexibilitythan that of conventional polyamides is required and there are used polyamide elastomers synthesized from a polyamide and a polyether.

Such polyamide/polyethercopolymers, however, lose their useful properties at a low temperature such as from 0 Cto 40"C. Also the oil resistance is lowered by their polyether constituent.

It has been found that by bonding a polyamide with a polysiloxane by amide linkage or ester linkage, there may be made a novel polyamide/polysiloxane copolymer having a good heat resistance, waterabsorption resiliance and chemical resistance, as well as excellent properties usual in polyamide resins such as mechanical properties, abrasion resistance, gasoline resistance and lubricant oil resistance.

According to the presentinvention,there is provided a polyamide-polysiloxane copolymercompris- ing a polyamide constituent (A) having repeating units of general formulae (I) and/or (ill):

wherein n is an integerfrom 5 to 11 x is a C6-C12 alkylene radical and Y is a C4-C10 alkylene radical, and amino groups or carboxyl groups at both terminals, and a polyorganosiloxane constituent (B) ofgeneralformula (Ill)::

wherein I is an integer from 2 to 50, mis an integer from 1 to 6, Q is an oxygen atom or a direct bond, R' is a hydrogen atom, a methyl group or a phenyl group, R is a divalent organic radical and Z is a hydroxyl group, an aminogroup ora carboxyl group,the constituents (A) and (B) being polymerized byamide linkages or ester linkages to give a straight chain polyamide copolymer having a J-value of 10-600 ml/g.

The polyamide copolymers of this invention have improved mechanical strength and plasticity at low temperature, hydrolysis resistance, heat resistance, oil resistance, chemical resistance, blood coagulating property compared with conventional polyamide resins or elastomers.

The polyamide copolymers ofthis invention are useful for separation film, being usable not only at ambienttemperature but at low or high temperature.

They may also be used as hot-melt adhesives, fibres, films and for molding and also as biopolymers.

The invention will be described more particularly in Examples set out below, the Examples being illustrated with reference to the accompanying drawings, in which Figures 1-12 are graphs showing IR charts of the polyamide copolymers obtained respectively in Examples 1-12.

The repeating units of formulae (I) and/or (II) in the polyamide constituent (A) ofthe copolymers may be formed from various polyamide-forming monomers described below.

There may be used as the polyamide-forming monomers C6C12 w-lactams and C6-C12 w-aminocarboxylic acids. More particularly the wlactams may be caprolactam, oenantholactam, decalactam, undecalactam or dodecalactam (laurolactam).

The w-aminocarboxylic acids may be 6 - amino caproic acid, 8-amino capric acid, 10-amino decanoic acid, 11 - amino undecanoic acid or 12 amino dodecanoicacid.

Asthe polyamide-forming monomers forming the repeating units offormula (Il), there can be used salts of C6-C12 diamines with C6- C12 dicarboxylic acids More particularlythe diamines may be salts of hexamethylene - diamine, undecamethylene - diamine or dodecamethylenediamine,whilethe acids may be adipic acid, azelaic acid, sebacic acid or dodecane dicarboxylic acid.

These polyamide-forming monomers may be used individually or any two or more ofthem may be used in combination.

Thepolyamideconstituent(A) should haveamino groups or carboxyl groups at both terminals and may be prepared by adjusting the terminals of a polyamide obtained from the above polyamideforming monomer(s). The adjustment ofthe terminals is usually carried out by reacting a dicarboxylic acid or diamine with the amino group orthe carboxyl group in equivalent amounts. For this purpose various dicarboxylic acids and diamines may be used, examples ofwhich are mentioned hereinafter as examples ofthe third constituent (C). Polyamides having repeating units offormula (II) may also be obtainedfromthe same diamineand dicarboxylic acid which are used fortheformation of the polyamides by using either one ofthem in excess.

Preferably polyamide constituents (A) are prepared by adjusting the terminals with a C6C12 dicarboxy- lic acid or diamine. As examples, there may be used a diamino terminated polyamide modified with hexamethylenediamine, a dicarboxyl terminated polyamide modified with adipic acid, a dicarboxyl terminated polyamide modified with dodecane dicarboxylicacid, and the like. Such adjustment ofthe terminals, however, may be effected simultaneously with the copolymerization step, when the amount of the dicarboxylic acid or diamine may be controlled to actasa molecularweightadiusting agent.

The polyorganosiloxane constituents (B) of formula (III) maybe divided intothreetypes, ofthe following formulae (111)-1, (111)-2, and (111)-3:

Constituent (B) is selected from these three types such that it may be condensed by amido linkages or ester linkages with the polyamide constituent (A). For example, when a diamino terminated polyamide is used, a dicarboxyl terminated polyorganosiloxane of formula (111)-2 is used (whereby amido linkages are formed). When a dicarboxyl terminated polyamide is used, a dihydroxyl terminated polyorganosiloxane of formula (111)-1 ora diamino terminated polyorganosiloxane offormula (111)-3 is used (whereby ester linkages oramido linkages are formed, respectively).

In the formula (III), R represents a divalentorganic radical which may suitably be an alkylene radical which may be branched, a polyoxyalkylene (C1 - C4) radical having a number average molecularweightof 50-3000, preferably 50-1000, a divalent alicyclic radical or divalent aromatic radical. As the divalent alicyclic radical a divalent radical containing an alicyclic hydrocarbon group may be used, and as the divalent aromatic radical a divalent radical containing an aryl group may be used.

The preferred alkylene radical is a straight chain or branched C2- C36 alkylene group. Forthe branched alkylenegroup, there may be used for example, groups oftheformule

Forthe polyoxyalkylene radical, there can be used groups ofthe formulae xCH2CH2ot CH2CH2-, -(CHCH3CH2O)y-CHCH3CH2-, etc, The divalent alicyclic radical may be a group ofthe formula

orthe like, which may further be substituted by lower alkyl g roup(s). Examples ofthe divalentaromatic radical are groups oftheformulae

which mayfurther be substituted by lower alkyl group(s). The divalent aromatic radical may contain an ether linkage, a sulphonyl linkage, a sulphide linkage or a carbonate linkage, as exemplified by groups oftheformulae

In each of the radicals mentioned above, hydrogen atom(s) may be substituted by halogen atom(s).

In formula (III) R' represents a hydrogen atom, a methyl group ora phenyl group. Although the radicals R' are usually the same, they can be different.

The constituent (B) offormula (III) may comprise a single compound ora mixture. it is preferable to use a combination of one of low molecularweight (for example 1=2 and m=1-2 orl=3and m=1) and one of high molecularweight (for example 1=5-50 and m=1-6orl=3-4andm=2-6).Thereisa tendency that, as the molecularweight of the organosiloxane moiety in constituent (B) increases, the compatibility ofthe constituent (B) with constituent (A) decreases and the J-value ofthe resulting copolymer becomes very low. However, the compatibility is improved and the J-value increases (the resulting copolymer becomes more elastic) by using anotherconstituent (B) having an organosiloxane moiety of low molecular weight.It is believed that the presence of the low molecu lar weig ht moiety facili- tatesfree rotation of the main chain of the resulting copolymer. The ratio of low molecularweight constituentto high molecularweightconstituent is suitably a molar ratio of :99-99: 1,preferably,10:90-90 : 1 O.

Typical polyorganosiloxane constituents (B) are available under the name "dihydroxyterminated, dicarboxyl terminated or diamino terminated polyorganosiloxane, and modifications thereof".

There are two processes known forthe method of polymerization.

1 A process which comprises first preparing a polyamide constituent (A) by polymerization and then coplymerizing (A) with a polyorganosiloxane constituent (B) (two step method).

2 A process which comprises coplymerizing a polyamide-forming monomerforthe polyamide constituent (A) with the polyorganosiloxane constituent (B) (one step method).

The polyamide copolymers obtained bythetwo step method have a polyamide moiety of blocktype, and the number average molecularweight oftheir polyamide blocks is suitable 500 -- 50000, preferably, 1000-10000. In contrast, the polyamidecopolymers obtained by the one step method have a random polyamide moiety.

In the two steps method, a polyamideconstituent (A) is copolymerized with the stoichiometrically equivalent amount of a polyorganosiloxane constituent (B) by ester linkage. The reaction is performed in the presence of an ordinary esterification catalyst at a temperature of about 170-270 C under atmospheric pressure for about 1-4 hours in the presence of an inert gas, (or 1-6 hr under vacuum).

The reaction mixture is then heated at a temperature of 200270 C under a reduced pressure of 30mmHg or lower, preferably, 10 - 1 5mmHg to expedite the polycondensation, and further at a temperature of 220-2700C under a reduced pressureoflmmHg or lower, preferably, 0.1 mmHg or lower. When the copolymerization is performed byamido linkage, the reaction for polycondensation may be carried out at a temperature of about 1 700270 C under atmospheric pressure in the presence of an inert gas, in the same manner as described above, but without using any catalyst.

In the one step method, a polyamide-forming monomer is reacted with a dicarboxylic acid or diamine for adjusting the terminals of the polyamide, and a polyorganosiloxane constituent, both in a stoichiometrically equivalent amount, in the manner described above.

As the esterification catalyst there may be used catalyst of the tin series, titanium series and lead series. These may be, for example, dialkyl tin oxides such as dibutyl tin oxide, dioctyl tin oxide; dialkyl tin alkylates such as dibutyl tin laurylate, dibutyl tin bis (2 -ethylhexanoate); tetraalkyl titanates such astetrabutyl titanate, tetraisopropyl titanate, titanium oxalates such as titanium potassium oxalate; lead compounds such as lead acetate. It is preferable to employ tin containing catalysts.

The polyamide copolymers embodying the present invention have a J-value of 10-600, preferably, 20300. The J-value [ml/g] is an index for evaluating the solution viscosity of a polymer, which is indirectly dependant on the molecularweight ofthe copolymer.

The J-values are determined according tothefollow- ing method [Deutsche Industrienorm (DIN) 16779Teil 2]: In a 50 ml volume measuring flask, 0.25g of a sample is weighted accurately and dissolved in a mixed solvent consisting of phenollo - dichlorobenzene (1/1) at room temperature or at an elevated temperature.

The volume is adjusted to 50ml.Then, dropping time is measured at 25 C by means of a Ubbellohde viscometer, with respect to the solvent only and to the solution ofthe sample. J-values are calculated according to the following equation: (dropping time of the solution/dropping time of the solvent only)-1 J-value= [mI/gi concentration of the sample (=0.5g/ml) dropping time of the solution #rel (realtive viscosity) dropping time of the solvent only.

The copolymers embodying the present invention comprise substantially a straight chain polymer wherein equivalent amounts of a polyamide constituent (A) and a polyorganosiloxane constituent (B) are connected byamido linkagesoresterlinkages.

The constituent (A) and/orthe constituent (B) may be interchanged partially with a third constituent (C) comprising one or more compound oftheformula (IV): J-R"-J (IV) whereinJ is a hydroxyl group, an amino group ora carboxyl group and R" is an alyklene radical, optionally branched, a divalent alicyclic radical or a divalent aromatic radical.

The R" radical may contain one or more hetero atom(s) and its hydrogen atom(s) may be substituted by halogen atom(s).

Thethird constituent (C) may be used in a ration of 70molar% or less, preferably 1 -70molar%, in relation to the polyamide constituent (A), and in a ratio of 99molar% or less, preferably 1 -99molar%, in relation to the polyorganosiloxane constituent (B).

Advantageouslythethird constituent is present in a ratio of3-97molar%, particularly 1095molar% in relation to constituent (B). The constituent (C) is useful for adjusting the mechanical strength of the copolymer. The third constituent (C) also serves the purpose of making the constituent (A) and the constituent (B) compatiblewith one another. When the ratio of interchange for constituent (B) exceeds 99molar%, properties ofthe copolymer resulting from constituent (B) are not obtained.In contrast, when the ratio is less than 1 molar%, the compatibility of constituent (B) with constituent (A) on their esterification reaction oramide-forming reaction may be reduced, the molecularweight ofthe resulting copolymer may be lower and the J-value may be less than 10. When the ratio of interchange with constituent (A) exceeds 70molar%, properties of the copolymer resulting from constituent (A) are not obtained. In contrast, when said ratio is less than 1 molar%,the molecular weight ofthe resulting copolymer may be lower. It is possible partially to interchange both constituent (A) and constituent (B) with a suitable common third constituent (C).

The third constituent (C) may be divided by the functional group into three types having formulae (IV)-1, (IV)-2 and (IV)-3: HOR"-OH (IVS1 HOOC-R11-COOH (IV)-2 H2N-R11-NH2 (IV)-3 Usually, a third constituent (C) having the same functional groups as the constituent (A) or (B) to be interchanged is employed. However, it is also possibleto use one having differentfunctional groups. For example, a third constituent (C) of diamine type may be usedto replace partially a constituent (B) of diol type, in addition to a third constituent (C) of diol type.

A mixtured of third constituents (C) ofdiamine type and diol type may also be used.

Third constituents (C) of formulae (IV)-2 or (IV)-3 may be used for adjusting the terminals ofthe polyamide constituent (A).

In the formula (IV), R" is an alkylene radical, optionally branched, a polyoxyalkylene (C1 - C4) radical having a number average molecularweightof 50-3000, preferably 50-1000, a diva lent alicyclic radical or a divalent aromatic radical which may contain an ether linkage, a sulphonyl linkage, a sulphide linkage or a carbonate linkage. In each radical, hydrogen atom(s) may be substituted by halogen atom(s). As examples of the radical R", there may be used,forexample, the groups illustrated for the radical R in formula (III).

Preferred examples ofthethird constituent (C) represented byformula (IV)-1 are C-36 aliphatic diols such as ethylene glycol, propyleneglycol, 1,4butylene glycol, 1,3-butylene glycol, 1,12-dodecane diol, alicyclic diols such as cyclohexane dimethanol; and polyalkylene glycols having a number average molecular weight of 50-3000, preferably of 300-3000, such as polypropylene glycol, polytetramethylene glycol or poly-2-methylpropylene glycol.

Preferred examples of dicarboxylic acids of formu la (IV)-2 are C2-C36 aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecane dicarboxylic acid, 1,4-cyclohexanedicarboxylicacid, dimeracid, and aromatic dicarboxylic acids such asterephthalic acid or isophthalic acid.

Preferred examples of diamines offormula (IV)-3 are C6- C36 aliphatic diamines such as ethylene diamine, trimethylene diamine, tetra methylene di amine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, dimer diamine (amino compound of a dimer of unsaturated fatty acid such as oleic acid, linolic acid, linolenic acid), 2,2,4-/2,4,4-trimethyl-hexamethylene diamine; alicy clicdiaminessuch as 1,3/1,4-bix(aminomethyl) cyclohexane, bis (4,4-aminocyclohexyl)methane, isophorone diamine; and aromatic diamines such as xylene diamine or diaminodiphenylmethane.

The ratio by weight ofthe constituents (A) : (B): (C) in the copolymers embodying the present invention is preferably 99-1: 1-99: 0-30, more particularly, 99-50 :1-50 : 020.

The present invention is further explained hereinaf terinthefollowing non-limiting Examples.

EXAMPLE 1 In a cylindertype flask of 11 volume were charged: 409 (0.04mol) of dicarboxyl terminated polyamide 12 modified with dodecane dicarboxylic acid (Mn = 1,000) as constituent (A); 4.3g (0.002mol : Smolar%) of dibutanoloxyterminated polydimethysiloxane (Mw = 2,132) as constituent (B); and 3.49 (0.038mol: 95molar%) of 1,4-butane-diol as constituent (C) partially replacing constituent (B). 0.02g of dibutyl tin oxide (Bu2SnO) was added as catalyst. The mixture in the flaskwas heated at 240 C on a metal bath while introducing nitrogen gas and stirred for 2 hours.

Then, the temperature was elevated to 270 C and the stirring was continued for one hour under a reduced pressure (bywaterjet pump) in the region of 1 5mmHg. The stirring was continued for another hour under a vacuum of 0.05mmHg (by high vacuum pump) while maintaining the temperature at 2700C.

The product obtained, taken out under nitrogen atmosphere, was a white, highly viscous polymer having the following characteristic values. Tg (glass transition temperature) and Tm (melting point) were measured using a DSC (MettlerTA-2000 type or Perkin-Elmer2Ctype): IR: 1745 (ester linkage between polyamide and polydimethylsiloxane and the third constituent), 1260,1100-1000 and 800 Cm~1 (absorptions char acteristic of polydimethylsiloxane), 1 NMR: 0.1 ppm (signal from the dimethyl group bonded to the silyl group of polydimethylsiloxane), J-value:81 ml/g Tg:9'C.

Tm :151 C.

From the results of measurement of Torsional vibration, it has been found thatthere is a second glass transition temperatu re at 123 C.

Figure 1 shows a chart of the above IR.

EXAMPLE 2 Polymerization was carried out using 209 (0.02mol) of dicarboxyl terminated polyamide 12 (Mn = 1000) as constituent (A), 2.02g (0.002mol :1 0molar%) of dibutanoloxyterminated polydimethylsiloxane (Mw = 1,005) as constituent (B), 1.62g (0.018moi: 90molar%) of 1,4-butanediol as constituent (C) and 0.01 g of dibutyl tin oxide as catalyst, underthe same conditions and using the same polymerization apparatus as Example 1.

Characteristic values ofthe polymer obtained are shown in the following: IR:1745 (ester linkage between polyamide and polydimethylsiloxane and the third constituent, 1265,110-1000 and 800cm-1 (absorption charac teristic of polydimethylsiloxane), 7H-NMR :0.1 ppm (signal from the dimethyl group bonded to the silyl group), J-value: 78ml/g, Tg : unclear Tm: 1530C Figure 2 shows a chart of the above IR.

EXAMPLE 3 Polymerizationwascarried out using 209 (0.00286mol) of dicarboxyl terminated polyamide 12 (Mn = 7,000) as constituent (A), 1 .84g (0.00286mol) of dibutanoloxyterminated polydimethylsiloxane (Mw = 645) as constituent (B) and 0.01 g of dibutyl tin oxide as catalyst, underthe same conditions and using the same polymerization apparatus as Example 1. The polymer obtained had a J-value of 148ml/g, and Tm of 178 C, although itsTG was unclear.

Figure 3 shows a chart of IR of the polymer obtained. From the results of measurement of mechanical characteristics by the method of DIN 53455, itwas observed that the polymer obtained has a Tensile Modulus of 1402N/mm2 and Elongation at break of 20%.

EXAMPLE 4 Polymerization was carried out using 209 (0.02mol) of dicarboxyl terminated polyamide 12 (Mn = 1,000) as constituent (A), 3.87g (0.006mol 30 molar%) of dibutanoloxyterminated polydemethysiloxane (Mw =645)as constituent (B), 1.26g (0.014 mol: 70molar%) of 1,4-butanediol as constituent (C) and 0.029 of dibutyl tin oxide as catalyst, under the same conditions and using the same polymerization apparatus as Example 1. The polymer obtained had a J-value of 111 ml/g and Tm of 151 C although its Tg was unclear.

Figure 4 shows a chart of IR of the polymer obtained. The polymer obtained has a Tensil Modulus of 245N/mm2 and Elongation at breakof 78%.

EXAMPLE 5 Polymerization was carried out using 40g (0.01 mol) of dicarboxyl terminated polyamide 12 (Mn = 4,000) as constituent (A), 1 .05g (0.0005mol : Smolar%) of didodecanoloxyterminated polydimethylsiloxane (Nw = 2,105) as a constituent (B), 0.86g (0.0095 mol: 95molar%) of 1,4-butanediol as constituent (C) and 0.039 of dibutyl tin oxide as catalyst, by means ofthe same polymerization apparatus and under the same conditions as Example 1.

Characteristic values of the polymer obtained are shown inthefollowing: Ir: 1743 (ester linkage between polyamide 12and polydimethylsiloxane and 1,4-butanediol, 1275 1100-1000 cm-1 (absorption characteristic of polydimethylsiloxane), H-NMR:0.1 ppm (signal from the dimethyl group bonded to the silyl group), J-value:79 ml/g.

Tg : unclear.

Tm: 172 C.

Figure 5 shows a chart ofthe above IR.

EXAMPLE 6 Polymerization was carried out using 309 (0.03mol) of dicarboxyl terminated polyamide 12 (Mn = 1,000) as constituent (A), 3.52g (0.0015mol): Smolar%) of dipropylaminoterminated polydimethylsiloxane (Mw = 2.345) as constituent (B) and 4.859 (0.0285mol = 95 molar%) of isophorone diamine as coinstituent (C) and without using any catalyst, underthe same conditions and using the same polymerization apparatus as Example 1.

Characteristic values of the polymer obtained were as follows: IR:1260, 1100-1000 and 800cm-1 (absorption characteristic of polydimethylsiloxane), 1H-NMR 0.1 ppm (signal from the dimethyl group bonded to the silyl group), J-value:83ml/g Tg : 37- 50"C.

TM:145 C, Further, from the results of measurement of Torsionalvibration, it has been foundthatthere is a second glass transition temperature at - 140 C.

Figure 6 shows a chart ofthe above IR.

EXAMPLE 7 Polymerization was carried out using 24.99 (0.01mol) of diamino terminated polyamide 12 (Mn = 2,490) as constituent (A), 1,45g (5molar%) of modified polyorganosiloxane (Mw = 2,899) ofthefollowing formula:

which has been prepared by introducing dodecane dicarboxylic acid residue to both terminals of a diaminoterminated polyorganosiloxane (Mw = 2,341) as constituent (B) and 2.199 (95molar%) of dodecane dicarboxylic acid as constituent (C) and without using any catalyst, underthe same conditions and with the same polymerization apparatus as Example 1.

Characteristicvaluesofthe polymer obtained were as follows: IR:1260, 1100-1000 and 800cm-1 (absorption characteristic of polydimethylsiloxane), H-NMR:0.1ppm (signal from dimethyl group bonded to the silyl group), J-value: :211 ml/g.

Tg : 30-450C.

Tm:167 C.

From the results of measurement of Torsional vibration, it has been found that there is a second glass transition temperature at - 123 C. The polymer obtained has aTensil Modulus of 480 N/mm2 and an Elongation at break of 287% .

Figure 7 shows a chart of the above IR. EXAMPLE 8 Polymerization was carried out using 209 (0.01 mol) ofdiamino terminated polyamide 11 (Mn = 2,000) as constituent (A), 1 .50g (5molar%) of the modified polydimethylsiloxane (Mw= 2,899) used in Example 7 as constituent (B) and 2.199 (95molar%) of dodecane dicarboxylic acid as constituent (C), without any catalyst, underthe same conditions and with the same polymerization apparatus as Example 1.

Characteristic values ofthe polymer obtained were as follows: IR:1265,1100-1000 and 850cm-1 (absorption characteristic of polydimethylsiloxane), H-NMR : ppm (signal from the dimethyl group bondedtothesilylgroup), J-value: 136ml/g.

Tg : unclear.

Tm: 1770C.

Figure 3 shows a chart ofthe above IR.

EXAMPLE 9 Polymerization was carried out using 39g (0.03mol) of dicarboxyliv terminated polyamide 6 (Mn = 1,300) modified with adipic acid as constituent (A), 2.1 6g (0.003mol : 90molar%) of dibutanoloxy terminated polydimethylsiloxane (Mw = 719) as constituent (B), 2.439 (0.027mol 10molar%) of 1,4-butanediol as constituent (C) and 0.029 of dibutyl tin oxide as catalyst, using the same polymerization apparatus and underthe same conditions as Example 1.

Characteristic value of the polymer obtained were as follows: H-NMR: : 1.1 ppm (signal from the dimethyl group bonded to the silyl group), J-value : 49ml/g.

Tg : 12-22 C.

Tm: 186 C.

From these values, it is noted that the polymer obtained is a copolymer of polyamide 6 and polydimethylsiloxane.

Figure 9 shows a chartofan IR carried out on the copolymer.

EXAMPLE 10 Polymerization was carried out using 30g (0.03mol) of dicarboxyl terminated polyamide 6 (Mn = 1,000) as constituent (A), 7.04g (0.003mol : 10molar%) of dipropylamino terminated polydimethylsiloxane (Mw = 2,345) as constituent (B) and 5.359 (0.027mol: 90molar%) of diaminodiphenylmethane as constituent (C), using the same polymerization apparatus and underthe same conditions as Example 1.

Characteristic values ofthe polymer obtained were as follows: 1H-NMR: : O.lppm (singal from thedimethyl group bondedtothesilyl group), Tg: 57-65 C.

Tm : unclear J-value : 68Ml/g.

The polymer obtained has a Tensile Modulus of 709N/mm and an Elongation at break of 39%.

IR chart of the copolymer is shown as Figure 10.

EXAMPLE 11 In a cylindertype flask of 1 volume were charged 209 of dicarboxyl terminated polyamide 12 (M = 1,000) as constituent (A), 6.07g (35molar%) of di-2methylpropanoloxyterminated polydimethylsiloxane (Mw = 867) and 4.039 (65molar%) of 2-methylpropanoloxytetramethyl disiloxane (Mw = 310) as constituent (B) and 0.029 of dibutyl tin oxide as catalyst. The mixture in the flask was heated at 240 C on a metal bath while introducing nitrogen gas, and stirred for 2 hours. Then the temperature was raised to 270 C and the stirring was continued for 1.5 hours under a reduced pressure (bywaterjetpump) of about 1SmmHg.Under a vacuum of 0.05mmHg (by high vacuum pump) the stirring was continued for a further2 hours while maintaining thetemperature at 270 C. As taken out under nitrogen atmosphere, the product obtained was a white, highly viscous polym erhavingthefollowing characteristic values: IR : 1745 (absorption bythe ester linkage between organosiloxane and polyamide), 1260,1100-1000 and 800cm- (absorption by polydimethylsilo xane).

1 H-NMR: : 0.1 ppm (signal from the dimethyl group bonded to the silyl group of polydimethylsiloxane), J-value: 188ml/g.

Tg : unclear.

Tm: 1490C An IR chart of the copolymer produced is illustrated in Figure 11.

EXAMPLE 12 In a cylinder type flask of 11 volume were charged 21.969 (90molar%) ofdiaminoterminated polyamide 12 (Mw = 2,440) and 10g (lOOmolar%) of dicarboxyl terminated polyamide 12 (Mw = 1,000) as constituent (A), and 2.359 (10molar%) of propylamine polydimethylsiloxane (Mw =2,345) as constituent (B).

The mixture was heated to 200 C and stirred for 1 hour,while introducing nitrogen gas. The temperaturewasthen raised to 250 C and stirring was continued for 0.5hour under a reduced pressure (by waterjet pump). The stirring was continued for 1 hour at 270"C under a high vacuum of 0.01 mmHg or less.

The polymer obtained had a J-value of 226ml/g, Tg of-50 C, Tm of 168 C, a Tensile Modulus of 164 N/mm2 and an Elongation at break of 11%. An IR chart is shown on Figure 12.

EXAMPLE 13 In a cylindertype flask of 11 volume were charged 209 of dicarboxyl terminated polyamide 12 (Mw = 4,000) as constituent (A), 2.27g of dibutanoloxy terminated polydimethylsiloxane as constituent (B), 2.59 of 1,4- butanediol as constituent (C) and 0.01 g of dibutyl tin oxide as catalyst. The mixture was heated at 250 C for 2 hours under normal pressure with stirring, while introducing nitrogen gas. The stirring was continued at 250 C for 1 hour under a reduced pressure in the region of 20-30 mmHg (bywater jet pump),followed by stirring at270 Cfor2 hours under vacuum of 0.1 mmHg (by high vacuum pump) to give the copolymer ofthe present invention. The copolymer obtained had a J-value of 21 5ml/g,Tg of -70"C, andTm of 171 C.

In the above Examples 1-13,the number average molecularweightofeach polyamide constituentwas calculated from the concentration ofthe amino or carboxyl group on theirterminals, according to the following method: In the case of a terminal carboxyl group, the polyamide constituent was dissolved in warm benzyl alcohol and methanol was added to the solution. Titration was then effected with 0.1 M KOH/methanol at room temperature.

In the case of a terminal amino group, titration was effected in a similar manner to that above, at room temperature but with 0.1 M HC1/methanol.

The method of calculation was as follows: A x 0.1 x F x 10-3 terminal amino group (eq/g) = W A: amount (ml) of the titrant 0.1N-HC1 F: factor of 0.1N-HC1 W: amount (g) of the sample (A-B)x0.1xFx10-3 terminal carboxyl group (eq/g) = W Where A: amount(ml) of the titrant 0.1-KOH B: amount (mlofthetitrant0.1M-KOH at blank F:Factor of 1.1N-KOH Calculation of mean molecular weight 2 [terminal amino group (eq/g)] + [terminal carboxyl group (eq/q)] Table 1

Example 1 Example 2 Example 3 Example 4 Polyamide minal wt% wt% COOH wt% COOH wt% constituent (A) Repeting -[NH(CH2)11CO]- 83.5 -[NH(CH2)11CO]- 84.6 -[NH(CH2)11CO]- 91.6 -[NH(CH2)11CO]- 79.6 [The general unit formula (I) and/or the general formula (II)I *Mw 1000 1000 7000 1000 l 4 - 6 4 - 6 2 2 polyorganom 5 2 2 2 siloxane Q oxygen oxygen oxygen oxygen constituent (B) % OH OH OH OH 9.0 8.5 8.4 15.4 R CH3 CH3 CH3 CH3 [The general formula (III)] R -C4H8- -C4H8- -(CH2)4- -C4H8 *Mw 2132 1005 645 645 The third J OH OH - OH constituent - (C) (The general R -C4H8- 7.1 -C4H8- 6.9 formula (IV)] J-value (ml/g) of polyamide copolymer 81 78 | 148 111 *Mw:Number average molecular weight Table 1 (cont'd)

Example 5 Example 6 Example 7 Example 8 Both text COOH COOH NH2 NH2 minal wt% wt% wt% wt% Polyamide constituent (A) Repeteating -[NH(CH2)11CO]- 95.4 -[NH(CH2)11CO]- 78.2 -[NH(CH2)11CO]- 87.3 -[NH(CH2)11CO]- 84.5 unit formula (I) and/or the general formula (II)] *Mw 4000 1000 2490 2000 l 4 - 6 29 29 29 polyorganom 2 1 1 1.

siloxane constituent Q oxygen direct bond direct bond direct bond (B) Z OH NH2 NH2 NH2 2.5 9.2 7.6 9.2 [The general R4 CH3 CH3 CH3 CH3 formula (III)] R -C12H24- -C3H6- -C3H6- -C4H6 *Mw 2105 2345 2345 2345 The third J OH NH2 COOH COOH constituent [The general R6 -C4H8- 2.1 # -(CH2)10- 6.3 formula (IV)] CH3 CH2- 12.6 -(CH2)10- 5.1 J-value (ml/g) of 79 83 211 136 polymide copolymer *Mw: Number average molecular weight Table 1 (cont'd)

Example 9 Example 10 Example 11 Example 12 Both ter COOH COOH COOH NH2 COOH minal wt% wt% wt% wt% constituent (A) Repeating -[NH(CH2)5CO]- 89.4 -[NH(CH2)5CO]- 70.8 -[NH(CH2)11CO]- 66.4 -[NH(CH2)5CO]- -[NH(CH2)11CO] [The general unit formula (I) and/or the general formula (II)] *Mw 1300 1000 1000 1440 1000 l 4 - 6 29 4 - 6 1 29 polyorgano- m 2 1 2 1 1 siloxane constituent Q oxygen direct bond oxygen oxygen direct bond (B) % OH NH2 OH OH NH2 5.0 16.6 CH3 CH3 33.6 6.8 [The general R' CH3 CH3 CH3 formula (III)] R -CH@CHCH@- -CH@CHCH@ -C4H6 -C3H6- CH@ CH@ -C3H6- *Mw 719 2345 867 310 2345 The third J OH NH2 - constituent (C) (The general R" -C4H8- 5.6 -#-CH2-#- - - - formula (IV)] J-value (nl/g) of polyamide copolymer 49 68 188 226 MW: Number average molecular weight

Claims (11)

1. A polyamide-polysiloxane copolymercompris- ing a polyamide constituent (A) having repeating units of general formulae (I) and/or (II): -[NH(CH2)nCO]- (I) -[NHXNHCOYCO]- (II) wherein n is an integer from 5 to 11,X a C6-12 alkylene radical and Y is a C4-C10 alkylene radical and amino groups or carboxyl groups are both terminals, and a polyorganosiloxane constituent (B) of general formula (III)::

wherein I is an integerfrom 2 to 50,n mis an integer from 1 to 6, Q is an oxygen atom or a direct bond, R' is a hydrogen atom,a methyl group ora phenyl group, R is a divalent organic radical and Z is a hydroxyl group, an amino group or a carboxyl group,the constituents (A) and (B) being polymerized by amide linkages or ester linkages to give a straight chain polyamide copolymer having a J-value of 10-600 ml/g.

2. A copolymer as claimed in claim 1, wherein the polyamide constituent (A) comprises a block polyamide moiety having a number average molecularweight of 500-50000.

3. A copolymer as claimed in claim 1 wherein the polyamide constituent (A) comprises a random polyamide moiety.

4. A copolymer as claimed in any one of the preceding claims, wherein R is an alkylene radical, optionally branched, a polyalkylene (C1-C4) radical having a number average molecularweight of 503000, a divalent alicyclic radical or a divalent aromatic radical optionally containing an ether linkage, a sulphonyl Iinkage,asulphidelinkageoracarbonate linkage.

5. A copolymer as claimed in claim 4, wherein one or more hydrogen atoms in said radicals are substituted by a respective one or more halogen atoms.

6. A copolymer as claimed in any one of the preceding claims, wherein the repeating units of formula (I) are formed by ring cleavageofa C6- C12 w-lactam or by condensation of a C6- C12 w-amino carboxylic acid.

7. A copolymer as claimed in any one of the preceding claims, wherein the repeating units of formula (II) are formed by condensation of C6- C12 diamine with a C6- C16 dicarboxylic acid.

8. A copolymer as claimed in any one of the preceding claims, further comprising athird constituent (C) offormula (IV): J-R"-J (IV) wherein J is a hydroxyl group, an amino group or a carboxyl group and R" is an alkylene radical optionally branched, a polyoxyalkylene (C1-C4) radical having a number average molecular weight of 50-3000, a divalent alicyclic radical or a divalent aromatic radical optionally containing an ether linkage, a sulphonyl linkage, a sulphide linkage ora carbonate linkage, said third constituent (C) replacing part of either the polyamide constituent (A) in a ratio of 70 molar % or less the polyamide constituent (a) and/or the polyorganosiloxane constituent (B) in a ratio of 99 molar % orless.

9. A copolymer as claimed in claim 8, wherein the ratio of interchange ofthethird constituent (C) forthe polyorganositoxane constituent (B) is3-97 molar %.

10. A copolymer as claimed in either claim 8 or claim 9, wherein the ratio of interchange ofthethird constituent (C) for the polyorganosiloxane constituent (B) is 10-95molar%.

11. A polyamide-poiysiloxane copolymer sub stantial ly as described herein with reference to the Examples.