CN101970536B - Carbodiimide-modified soluble polyamide, method for producing the same, and carbodiimide-modified soluble polyamide solution - Google Patents
Carbodiimide-modified soluble polyamide, method for producing the same, and carbodiimide-modified soluble polyamide solution Download PDFInfo
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Abstract
Disclosed is a carbodiimide-modified soluble polyamide obtained by reacting 100 parts by mass of a soluble polyamide and 0.5-20 parts by mass of a carbodiimide compound in the presence or absence of a solvent at a reaction temperature of 50-300 DEG C. This soluble polyamide is excellent in solubility, moisture resistance and heat resistance, while having good storage stability.
Description
Technical field
The present invention relates to Carbodiimide-Modified soluble polyamide and preparation method thereof and Carbodiimide-Modified soluble polyamide solution, in more detail, the Carbodiimide-Modified soluble polyamide solution that relates to solvability, wet fastness and thermotolerance are good and stability in storage is good Carbodiimide-Modified soluble polyamide and preparation method thereof and its dissolving is formed.
Background technology
Polyamide-based resin is owing to having good mechanical characteristics, thermotolerance, a resistance to chemical reagents, therefore as engineering plastics and useful as the formed body material of electronics and electric purposes, the mechanical purposes of OA (office automation), automobile purposes etc.In recent years, in order to improve the performances such as toughness of polyesteramide, studied the method (for example, with reference to patent documentation 1 and 2) of adding single carbodiimide or polycarbodiimide.But these polyamide-based resins are insoluble in alcohol and wait all kinds of SOLVENTS, and if not just not melting under the temperature more than 200 ℃, so formability is bad.
In addition, carried out various research and development as making the liquefiable technology of polymeric amide, for example, the technology of the hydrogen atom of known amido linkage of replacing various polymeric amide with the methoxy methyl base section.In addition, known by combined polyether on the skeleton of polymeric amide etc. reduce the amide group in the molecule concentration, improve deliquescent method.But such soluble polyamide because the concentration of the amide group in the molecule is low, is therefore compared with common polymeric amide, has the problem of thermotolerance and intensity difference and facile hydrolysis.
Therefore, also there is not the good soluble polyamide of solvability, wet fastness, thermotolerance and stability in storage.
Patent documentation 1: Unexamined Patent 6-298932 communique
Patent documentation 2: No. 3452563 communique of patent
Summary of the invention
The present inventor has studied by add carbodiimide compound in soluble polyamide and has improved solvability, wet fastness and stable on heating method, but added the soluble polyamide of carbodiimide compound, wet fastness and thermotolerance are insufficient, and the stability in storage of solution meeting variation, when the products formeds such as the rear formation of long-time storage film, find the homogeneity existing problems of products formed.
Therefore, the object of the present invention is to provide the good and good soluble polyamide of stability in storage of a kind of solvability, wet fastness and thermotolerance.
The present inventor has carried out repeatedly deep research in order to develop soluble polyamide with described preferred character.It found that, makes the reaction of soluble polyamide and carbodiimide compound and the Carbodiimide-Modified soluble polyamide that obtains can reach this purpose, and has finished the present invention based on this opinion.
That is, the present invention relates to:
(1) a kind of Carbodiimide-Modified soluble polyamide, this Carbodiimide-Modified soluble polyamide is by in the presence of solvent or not, under 50-300 ℃ temperature of reaction, makes the carbodiimide compound reaction of the soluble polyamide of 100 mass parts and 0.5-20 mass parts and obtains.
(2) a kind of preparation method of Carbodiimide-Modified soluble polyamide, it is characterized in that, the method be included under the existence of solvent or do not exist lower, under 50-300 ℃, make the soluble polyamide of 100 mass parts and the carbodiimide compound reaction of 0.5-20 mass parts.
(3) a kind of Carbodiimide-Modified soluble polyamide solution, this Carbodiimide-Modified soluble polyamide solution obtains by dissolving above-mentioned (1) described Carbodiimide-Modified soluble polyamide in solvent.
According to the present invention, can provide solvability, wet fastness and thermotolerance well and the good soluble polyamide of stability in storage.
Embodiment
Below, the present invention will be described in more detail.
Carbodiimide-Modified soluble polyamide of the present invention, for by in the presence of solvent or not, under 50-300 ℃ temperature of reaction, make the reaction of soluble polyamide and carbodiimide compound and the Carbodiimide-Modified soluble polyamide that obtains.
Employed soluble polyamide is mixture 100 mass parts with respect to mixture and/or the pure and mild ketone series solvent of pure and mild aromatic series series solvent among the present invention, can dissolve fully 1 mass parts above, be preferably that 5 mass parts are above, the above polymeric amide of 10 mass parts more preferably.
As described alcohol, can enumerate such as methyl alcohol, ethanol, Virahol etc., as described aromatic series series solvent, can enumerate such as benzene, toluene etc., as described ketone series solvent, can enumerate for example pimelinketone, 2-butanone, cyclopentanone.These alcohol, fragrant family and ketone series solvent are preferably boiling point and are the solvent below 130 ℃.
Object lesson as the mixture of described pure and mild aromatic series series solvent, can enumerate the mixture (mass mixing ratio is about 50: 50～3: 97) of methyl alcohol and toluene, as the object lesson of the mixture of described pure and mild ketone series solvent, can enumerate the mixture (mass mixing ratio is about 50: 50～10: 90) of methyl alcohol and pimelinketone.
Soluble polyamide among the present invention for example can obtain by making the polymeric amide solubilization.
As described liquefiable method, can be suitable known method, for example can enumerate the method for a part of the hydrogen atom of the amido linkage by replacing various polymeric amide with methoxymethyl.When introducing methoxyl group in polymeric amide, the hydrogen binding ability that amide group has can be lost, thereby hinders the crystallinity of polymeric amide, and therefore the solvability in solvent can increase.In addition, as described liquefiable method, can enumerate the method for introducing polyethers or polyester in the molecule of the polymeric amide before solubilization for example and forming multipolymer.As the polymeric amide before the solubilization, can enumerate nylon 6, nylon 66, NYLON610, （Fen Mo/Ke Li） Nylon11 in powder/granular form, nylon 12, nylon 46 etc.
As the object lesson of the soluble polyamide among the present invention, can enumerate Zytel 61 (デ ユ Port Application Co., Ltd. system), Versalon (ゼ ネ ラ Le ミ Le ズ society system), ア ミ ラ Application CM4000, CM8000 (eastern レ Co., Ltd. system), PA-100 (Fuji changes into Industrial Co., Ltd's system), ト レ ジ Application (Na ガ セ ケ system テ Star Network ス Co., Ltd. system) etc.
The carbodiimide compound that uses among the present invention, for having the carbodiimide compound of the carbodiimide groups more than 1 in the molecule, can enumerate single carbodiimide compound, polycarbodiimide compound etc., can be by general known method, for example, use organophosphorus based compound or organometallic compound as catalyzer, under the about temperature more than 70 ℃, in solvent-free or inert solvent, various polymeric polyisocyanates are carried out the decarboxylation condensation reaction and synthesize.
As above-mentioned single carbodiimide compound, can dicyclohexyl carbodiimide, di-isopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, tertiary butyl sec.-propyl carbodiimide, phenylbenzene carbodiimide, di-t-butyl carbodiimide, two-betanaphthyl carbodiimide etc. be shown example, wherein, particularly from considering preferred dicyclohexyl carbodiimide or di-isopropyl carbodiimide industrial aspect easily obtaining.
In addition, as above-mentioned polycarbodiimide compound, can use the polycarbodiimide compound of the preparation that ins all sorts of ways, basically, (for example can use the preparation method of utilization polycarbodiimide in the past, with reference to No. 2941956 specification sheets of United States Patent (USP), J.Org.Chem.28,2069-2075 (1963), Chemical Review 1981, Vol.81No.4, p619-621) and the carbodiimide compound of preparation.
Organic diisocyanate as the synthesis material in the preparation of polycarbodiimide compound, can enumerate for example aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, perhaps their mixture, specifically, can enumerate 1, the 5-naphthalene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 4,4 '-phenylbenzene dimethylmethane vulcabond, 1,3-phenylene diisocyanate (1,3-phenyleneisocyanate), 1, the 4-phenylene diisocyanate, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, hexamethylene diisocyanate, hexanaphthene-1, the 4-vulcabond, the xylylene vulcabond, isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, methylcyclohexane diisocyanate, tetramethyl-benzene dimethyl vulcabond, 2,6-diisopropyl benzene group diisocyanate, 1,3,5-triisopropylbenzene-2,4-vulcabond etc.
Wherein, consider from the viewpoint that improves flexible and wet fastness effect etc., preferred fat family (comprising alicyclic) organic diisocyanate, particularly more preferably isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, tetramethyl-benzene dimethyl vulcabond or two kinds mixture in them.
In addition, in the preparation of above-mentioned polycarbodiimide compound, can by cooling off polyreaction etc., make Halfway Stopping, thereby control the suitable polymerization degree.At this moment, end is isocyanate group.And, for the suitable polymerization degree of control, use in addition compound monoisocyanates compound etc. and terminal isocyanate group reaction polycarbodiimide compound, to all or part of method of carrying out end-blocking of residual terminal isocyanate group.By the control polymerization degree, can improve with the intermiscibility of soluble polyamide, improve stability in storage, improve on the quality this point preferred.
Carry out the monoisocyanates compound that end-blocking is controlled its polymerization degree as the end that is used for such polycarbodiimide compound, can such as phenyl isocyanate, tolyl isocyanic ester, xylyl isocyanic ester, cyclohexyl isocyanate, n-butyl isocyanate, naphthyl isocyanic ester etc. be shown example.
In addition, carry out the end-capped agent that end-blocking is controlled its polymerization degree as the end that is used for polycarbodiimide compound, be not limited to above-mentioned monoisocyanates compound, can the example illustrate can with the active dydrogen compounds of isocyanic ester radical reaction, for example (i) aliphatics, aromatic series or alicyclic compound have-methyl alcohol of OH base, ethanol, phenol, hexalin, N-Mono Methyl Ethanol Amine, poly glycol monomethyl ether, polypropylene glycol monomethyl ether; (ii) have=diethylamine of NH base, dicyclohexyl amine; (iii) have-NH
2Butylamine, the hexahydroaniline of base; (iv) have-succsinic acid of COOH base, phenylformic acid, cyclohexylenedinitrilotetraacetic acid; (v) have-sulfur alcohol of SH base, allyl mercaptan, thiophenol; (vi) has the compound of oxyethyl group; (vii) acid anhydrides such as diacetyl oxide, methyl tetrahydrochysene phthalate anhydride, methyl hexahydrophthalic acid anhydride etc.
The decarboxylation condensation reaction of above-mentioned organic diisocyanate is carried out in the presence of suitable carbodiimide catalyzer, as the carbodiimide catalyzer that can use, preferred organic phosphorus series compound, organometallic compound [formula M-(OR)
n[M represents titanium (Ti), sodium (Na), potassium (K), vanadium (V), tungsten (W), hafnium (Hf), zirconium (Zr), plumbous (Pb), manganese (Mn), nickel (Ni), calcium (Ca) or barium (Ba) etc., R represents that carbonatoms is the alkyl or aryl of 1-20, n represents the valence mumber of M] expression organometallic compound], especially consider from active aspect, preferred phospholene oxides (Phospholene oxide in the organophosphorus based compound, Off オ ス Off オ レ Application オ キ シ De) class, in addition, preferred hafnium in the organometallic compound, the pure salt of zirconium.
As above-mentioned phospholene oxides class, can 3-methyl isophthalic acid-phenyl-2-phospholene-1-oxide compound, 3-methyl isophthalic acid-ethyl-2-phospholene-1-oxide compound, 1 be shown example particularly, 3-dimethyl-2-phospholene-1-oxide compound, 1-phenyl-2-phospholene-1-oxide compound, 1-ethyl-2-phospholene-1-oxide compound, 1-methyl-2-phospholene-1-oxide compound or their double bond isomer, wherein, particularly preferably in the facile 3-methyl isophthalic acid-phenyl of industrial appearance-2-phospholene-1-oxide compound.
As carbodiimide compound, so long as in having the molecule of above-mentioned function, have the carbodiimide compound of the carbodiimide-based more than 1, just there is no particular limitation, consider from improving the aspects such as reactive and stability to hydrolysis resistance effect, preferred 4, the polycarbodiimide compound that has the carbodiimide-based more than 2 in the molecule of 4 '-dicyclohexyl methyl hydride carbodiimide etc., more preferably aliphatics or alicyclic ring family polycarbodiimide compound.In addition, the preferred 2-30 of the polymerization degree, more preferably 2-20.The polymerization degree is 2 when above, and is preferred on the thermotolerance this point, and the polymerization degree is 20 when following, with the intermiscibility this point of soluble polyamide on preferably.
(preparation of Carbodiimide-Modified soluble polyamide)
Carbodiimide-Modified soluble polyamide among the present invention, by in the presence of solvent or not, make the reaction of above-mentioned soluble polyamide and carbodiimide compound, the carboxyl that soluble polyamide has or amino isoreactivity functional group, obtain with the carbodiimide-based of the carbodiimide compound that can react with it or isocyanic ester radical reaction.
There is no particular limitation for the method for above-mentioned soluble polyamide and carbodiimide compound reaction, can carry out in the presence of solvent or not.
As the method for in the presence of solvent, reacting, for example, can enumerate the method for reacting after soluble polyamide and carbodiimide compound are dissolved in solvent, the method of preferably soluble polyamide and carbodiimide compound heated and stirred being reacted, add carbodiimide compound in the solution that more preferably obtains to dissolving soluble polyamide in solvent, and the method that heated and stirred is reacted under refluxing.Can by under normal pressure or the decompression under from the solution that obtains like this desolventizing obtain Carbodiimide-Modified soluble polyamide of the present invention.
As solvent not in the presence of the method for reacting, the method that can enumerate the method for after making the soluble polyamide melting more than the fusing point, mixing to react with carbodiimide compound, make soluble polyamide and carbodiimide compound melting mixing and react by biaxial extruder.
When making the reaction of soluble polyamide and carbodiimide compound, there is not the compound that hinders Carbodiimide-Modified in the preferred reaction system, the solvent that more preferably only has carbodiimide compound, soluble polyamide in the reaction system and use as required.As the object lesson of the compound that hinders above-mentioned Carbodiimide-Modified, can enumerate Resins, epoxy, amine is resin, melamine resin, phenolic resin etc.
Making the time of above-mentioned soluble polyamide and carbodiimide compound reaction, according to the kind of the soluble polyamide that uses, carbodiimide compound, reaction method, temperature of reaction etc. and different, for example is about 1-500 minute, is preferably 5-200 minute.
About making the temperature of above-mentioned soluble polyamide and carbodiimide compound reaction, according to the soluble polyamide that uses with carbodiimide compound and different, require as 50-300 ℃, when in the presence of solvent, making the reaction of soluble polyamide and carbodiimide compound, be preferably 50-150 ℃, more preferably 70-130 ℃.In addition, solvent not in the presence of when making the reaction of soluble polyamide and carbodiimide compound, be preferably 130-300 ℃, more preferably 150-280 ℃.During 50 ℃ of temperature of reaction less thaies, the thermotolerance of product, wet fastness and stability in storage are insufficient.In addition, when surpassing 300 ℃, easily cause the deterioration that is caused by the decomposition of resin etc.
In addition, react by above-mentioned make soluble polyamide and carbodiimide compound, soluble polyamide is modified, and becomes the Carbodiimide-Modified soluble polyamide.For example, be accompanied by the carrying out of above-mentioned reaction, the carbodiimide-based that carbodiimide compound has reduces, and therefore, when measuring comparison reactant and product by infrared rays, the peak of the carbodiimide-based of observing in the reactant has reduced in product.In addition, when carrying out the flow measurement of differential thermogravimetric for reactant and product, owing to amide resins reason and carbodiimide resinogen because of etc. observe the endotherm(ic)peak of a plurality of reactants, and the endotherm(ic)peak of product to compile be 1.Confirm that thus soluble polyamide of the present invention is modified.
Carbodiimide-Modified soluble polyamide obtained above is compared with the composition that is comprised of soluble polyamide and carbodiimide compound, and thermotolerance, wet fastness and stability in storage are good.Especially about stability in storage, when forming solution, can cause tackify or even the gelation of solution with respect to the situation of composition, even the soluble polyamide after the modification does not show the variations such as tackify yet under solution state, can standing storage under this state.
The addition of carbodiimide compound with respect to the soluble polyamide of 100 mass parts, is preferably the 0.5-20 mass parts, more preferably the 1-10 mass parts.During addition less than 0.5 mass parts, can not get wet fastness and stable on heating sufficient raising, when surpassing 20 mass parts, the plasticity-of the resin that obtains is too high, shock-resistance is impaired.
Carbodiimide-Modified soluble polyamide of the present invention in the scope of not damaging effect of the present invention, also can add other known additive.
The present invention also provides the preparation method of Carbodiimide-Modified polymeric amide, it is characterized in that, in the presence of solvent or not, under 50-300 ℃, makes the soluble polyamide of 100 mass parts and the carbodiimide compound reaction of 0.5-20 mass parts.
The preparation method's of Carbodiimide-Modified soluble polyamide of the present invention details is identical with the method for above-mentioned preparation Carbodiimide-Modified soluble polyamide of the present invention.
The present invention also provides the Carbodiimide-Modified soluble polyamide solution that obtains by dissolving Carbodiimide-Modified soluble polyamide of the present invention in solvent.
The solvent that uses in the Carbodiimide-Modified soluble polyamide solution of the present invention for example, can use the pure series solvents such as methyl alcohol, ethanol, Virahol; The ketone series solvents such as pimelinketone, 2-butanone, cyclopentanone; The acid amides such as dimethyl formamide, N,N-DIMETHYLACETAMIDE series solvent; Phenol series solvents such as aromatic series series solvent, phenol, the cresols such as ether series solvent, benzene, the toluene such as tetrahydrofuran (THF), diox or mix their two or more uses.
In addition, in the preparation of above-mentioned Carbodiimide-Modified soluble polyamide of the present invention, after in the presence of solvent, making the reaction of soluble polyamide and carbodiimide compound, even not desolventizing also can prepare Carbodiimide-Modified soluble polyamide solution of the present invention.
Embodiment
The present invention will be described in more detail by the following examples, but the present invention is not limited to these embodiment.
In addition, the condition determination in embodiment and the comparative example as described below.
(1) ir spectrophotometry is measured
Use fourier-transform infrared spectrophotometer (Shimadzu Scisakusho Ltd's system, model FTIR-8400S), the peak that makes the carbodiimide unit is 2150cm
-1～2100
-1, the variation of observation carbodiimide key.
(2) fusing point
Using differential scanning calorimetric measurement device (DSC, SII Na ノ テ Network ノ ロ ジ one society's system, DSC6200), is that 25 ℃ → 200 ℃, heat-up rate are to measure under 10 ℃/minute measuring temperature range.
(3) 5% loss of weight temperature
Using simultaneously determinator (TG-DTA, SII Na ノ テ Network ノ ロ ジ one society's system, TG/DTA6200) of differential thermogravimetric amount, is that 25 ℃ → 500 ℃, heat-up rate are to measure under 10 ℃/minute measuring temperature range.
Synthesis example 1 (synthesizing of carbodiimide compound)
Make 4 of 590g, the carbodiimide catalyzer of the cyclohexyl isocyanate of 4 '-dicyclohexyl methane diisocyanate, 62.6g and 6.12g (3-methyl isophthalic acid-phenyl-2-phospholene-1-oxide compound) was 180 ℃ of lower reactions 48 hours, obtain 4,4 '-dicyclohexyl methyl hydride carbodiimide resin (polymerization degree=10).
Embodiment 1
In 1 liter removable flask, add mixed solvent (mass mixing ratio is 4: the 6) 450.0g of ester copolyamide resin (trade name: CM-8000, eastern レ Co., Ltd. system) 50.0g and Virahol and toluene, stir and make it dissolving.In the solution that obtains like this, add the polycarbodiimide resin that obtains in the synthesis example 1 of 5.0g, flask is immersed in 120 ℃ the oil bath, and heated and stirred by the drying under reduced pressure desolventizing, obtained the Carbodiimide-Modified soluble polyamide after 3 hours under refluxing.
The Carbodiimide-Modified soluble polyamide that obtains is carried out ir spectrophotometry measure, confirm at 2120cm
-1The absorption peak that the existence that shows carbodiimide-based is arranged.In addition, the Carbodiimide-Modified soluble polyamide that obtains is carried out the differential scanning calorimetric measurement, observe 1 endotherm(ic)peak.And the second-order transition temperature of the Carbodiimide-Modified soluble polyamide that obtains is 120 ℃, and 5% loss of weight temperature is 320 ℃.
Embodiment 2
Adding the polycarbodiimide resin that obtains in the 5.0g synthesis example 1 in the powder of the solvability amide resins (trade name: PA-100 (Fuji changes into Industrial Co., Ltd)) of 100.0g is dry mixed.They are used laboratory stirrer (ラ ボ ミ キ サ one), after under 180 ℃ mixing 10 minutes, take out cool to room temperature, obtain the Carbodiimide-Modified soluble polyamide.
The Carbodiimide-Modified soluble polyamide that obtains is measured by ir spectrophotometry, at 2125cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates 1 endotherm(ic)peak, and second-order transition temperature is 110 ℃, and 5% loss of weight temperature is 322 ℃.
Embodiment 3
(trade name: ト レ ジ Application (Na ガ セ ケ system テ Star Network ス)) mixed solvent (mass mixing ratio is 3: the 7) 380.0g of 50.0g and methyl alcohol and pimelinketone, stirring makes it dissolving to add alkoxy-modified amide resins in 1 liter removable flask.Add the polycarbodiimide resin that obtains in the synthesis example 1 of 8.0g in the solution that obtains like this, heated and stirred by the drying under reduced pressure desolventizing, obtained the Carbodiimide-Modified soluble polyamide after 150 minutes in 80 ℃ oil bath.
The Carbodiimide-Modified soluble polyamide that obtains is measured by ir spectrophotometry, at 2120cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates 1 endotherm(ic)peak, and second-order transition temperature is 130 ℃, and 5% loss of weight temperature is 280 ℃.
Embodiment 4
In the ester copolyamide resin of 100.0g (trade name: CM-4000, eastern レ Co., Ltd. system)) toner in add the polycarbodiimide resin that obtains in the 8.0g synthesis example 1 and be dry mixed.It is used biaxial extruder, after mixing under 280 ℃, take out cool to room temperature, obtain the Carbodiimide-Modified soluble polyamide.
The Carbodiimide-Modified soluble polyamide that obtains is measured by ir spectrophotometry, at 2125cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates 1 endotherm(ic)peak, and second-order transition temperature is 145 ℃, and 5% loss of weight temperature is 322 ℃.
Embodiment 5
Mixed solvent (mass mixing ratio is 5: the 95) 330.0g that adds solvability amide resins (trade name: PA-105A (Fuji changes into Industrial Co., Ltd)) 45.0g and methyl alcohol and toluene in 1 liter removable flask stirs and makes it dissolving.Add the polycarbodiimide resin that obtains in the synthesis example 1 of 1.3g in the solution that obtains like this, heated and stirred by the drying under reduced pressure desolventizing, obtained the Carbodiimide-Modified soluble polyamide after 150 minutes in 100 ℃ oil bath.
The Carbodiimide-Modified soluble polyamide that obtains is measured by ir spectrophotometry, at 2120cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates 1 endotherm(ic)peak, and second-order transition temperature is 135 ℃, and 5% loss of weight temperature is 330 ℃.
Comparative example 1
Add the polycarbodiimide resin of 5.0g in nylon 6,6 resins of 100g, after mixing 10 minutes, cool to room temperature obtains the Carbodiimide-Modified soluble polyamide in 250 ℃ laboratory stirrer.
Comparative example 2
Directly use the ester copolyamide resin that uses among the embodiment 1.
Comparative example 3
Directly use the solvability amide resins that uses among the embodiment 2.
Comparative example 4
Except in embodiment 1, do not heat flask, and stir at normal temperatures, similarly to Example 1 operation obtains containing the polyamide resin of polycarbodiimide resin.
The polymeric amide that contains polycarbodiimide resin that obtains is measured by ir spectrophotometry, at 2120cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates a plurality of endotherm(ic)peaks, and second-order transition temperature is 100 ℃, and 5% loss of weight temperature is 280 ℃.
Comparative example 5
In embodiment 2, use laboratory stirrer, also mixing at normal temperatures, but therefore not melting of resin, can only become mixture, therefore, can not observe the variation of physical property.
Comparative example 6
Except in embodiment 3, do not heat flask, and stir at normal temperatures, similarly to Example 3 operation obtains containing the polyamide resin of polycarbodiimide resin.
The polymeric amide that contains polycarbodiimide resin that obtains is measured by ir spectrophotometry, at 2120cm
-1The place demonstrates the absorption peak of carbodiimide-based, by the differential scanning calorimetric measurement, demonstrates a plurality of endotherm(ic)peaks, and second-order transition temperature is 80 ℃, and 5% loss of weight temperature is 250 ℃.
Come the resin that obtains among Evaluation operation example 1-3 and the comparative example 1-6 with following benchmark, its result is as shown in table 1.
＜estimate
1, solvability
Be 4: 6 mixed solvent 100 mass parts with respect to the mass mixing ratio of methyl alcohol and toluene, add the resin that 10 mass parts obtain, at room temperature stirred 60 minutes.The situation that will become homogeneous solution is designated as zero, undissolvable situation is designated as *.In addition, measure the viscosity of the solution that obtains.
2, stability in storage
Under air-tight state, under 25 ℃ condition, the resin solution for preparing in the above-mentioned dissolubility test was placed 7 days, before and after placing, measure viscosity, the situation that will not have the viscosity 10% or more to increase is designated as zero, will have the situation of the viscosity increase more than 10% to be designated as *.
3, wet fastness
Being the thick films of 100 μ m with the resin forming that obtains, is to place 3 days under 85% the condition in 85 ℃ of temperature, humidity.Spring rate before and after measure placing is designated as zero with the situation of deficient change 10%, the situation more than 10% of being changed to is designated as *.
4, thermotolerance
Use differential scanning calorimetric measurement device (TG-DTA), measure the heat decomposition temperature of the resin that obtains.5% heat decomposition temperature is surpassed 300 ℃ is designated as zero, be designated as below 300 ℃ *.
5, viscosity
In the mixed solvent (mass mixing ratio is 40: 60) (solid component concentration is 12 quality %) of Virahol and toluene, use Type B rotational viscosimeter (Toki Sangyo Co., Ltd.'s system, VISCOTESTERTVB-10) to measure the viscosity under 25 ℃ under the solution state resin dissolves that obtains.
[table 1]
Table 1
[table 2]
Table 2
Industrial applicibility
Therefore modification polycarbodiimide composition of the present invention is suitable as the formed body materials such as electronics and electric purposes, OA machinery purposes, automobile purposes because solvability, wet fastness, thermotolerance and stability in storage are good.
Claims (7)
1. Carbodiimide-Modified soluble polyamide, this Carbodiimide-Modified soluble polyamide is by in the presence of solvent or not, under 50-300 ℃ temperature of reaction, make the carbodiimide compound reaction of the soluble polyamide of 100 mass parts and 0.5-20 mass parts and obtain, described soluble polyamide is with respect to the mixture of the pure and mild aromatic series series solvent of 100 mass parts and/or the mixture of pure and mild ketone series solvent, can dissolve the above polymeric amide of 1 mass parts fully.
2. Carbodiimide-Modified soluble polyamide according to claim 1, wherein, this Carbodiimide-Modified soluble polyamide is by in the presence of solvent, under 50-150 ℃ temperature of reaction, makes the reaction of described soluble polyamide and described carbodiimide compound and obtains.
3. Carbodiimide-Modified soluble polyamide according to claim 2, wherein, this Carbodiimide-Modified soluble polyamide is by the described carbodiimide compound of interpolation in the solution that obtains to the described soluble polyamide of dissolving in described solvent, and heated and stirred is reacted and obtained under refluxing.
4. Carbodiimide-Modified soluble polyamide according to claim 1, wherein, this Carbodiimide-Modified soluble polyamide by solvent not in the presence of, under 130-300 ℃ temperature of reaction, make described soluble polyamide and described carbodiimide compound the reaction and obtain.
5. the described Carbodiimide-Modified soluble polyamide of any one according to claim 1-4, wherein, described carbodiimide compound is aliphatics or alicyclic ring family polycarbodiimide compound.
6. the preparation method of a Carbodiimide-Modified soluble polyamide, it is characterized in that, the method be included under the existence of solvent or do not exist lower, under 50-300 ℃, make the soluble polyamide of 100 mass parts and the carbodiimide compound reaction of 0.5-20 mass parts, described soluble polyamide is with respect to the mixture of the pure and mild aromatic series series solvent of 100 mass parts and/or the mixture of pure and mild ketone series solvent, can dissolve the above polymeric amide of 1 mass parts fully.
7. Carbodiimide-Modified soluble polyamide solution, this Carbodiimide-Modified soluble polyamide solution obtains by the described Carbodiimide-Modified soluble polyamide of any one among the dissolving claim 1-5 in solvent.
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| JP2007278749 | 2007-10-26 | ||
| JP2007-278749 | 2007-10-26 | ||
| PCT/JP2008/068758 WO2009054312A1 (en) | 2007-10-26 | 2008-10-16 | Carbodiimide-modified soluble polyamide, method for producing the same, and carbodiimide-modified soluble polyamide solution |
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| JP5811337B2 (en) * | 2011-09-12 | 2015-11-11 | 国立研究開発法人産業技術総合研究所 | 2-pyrrolidone polymer or copolymer with modified physical properties |
| US10058502B2 (en) | 2015-12-31 | 2018-08-28 | L'oreal | Nail polish compositions |
| FR3073848B1 (en) | 2017-11-17 | 2020-11-13 | Arkema France | BLOCK COPOLYMER WITH IMPROVED RESISTANCE TO ABRASION AND TEARING |
| JP6799720B1 (en) * | 2019-03-22 | 2020-12-16 | 日清紡ケミカル株式会社 | Powdered polycarbodiimide compound and ester resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128599A (en) * | 1976-12-22 | 1978-12-05 | Celanese Corporation | Polyamides for extrusion applications |
| US6451890B1 (en) * | 1998-03-30 | 2002-09-17 | Nisshinbo Industries, Inc. | Polyamide resin composition |
| CN1938339A (en) * | 2004-03-26 | 2007-03-28 | 三井化学株式会社 | Novel resin modifier and polar group-containing polymer composition including same |
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| DE4214193A1 (en) * | 1992-04-30 | 1993-11-04 | Rhein Chemie Rheinau Gmbh | HYDROLYSTABLE POLYAMIDE |
| JPH06329795A (en) * | 1993-05-24 | 1994-11-29 | Sumitomo Bakelite Co Ltd | Production of partially imidized photosensitive poly(amic acid) ester |
| JPH11140164A (en) * | 1997-11-05 | 1999-05-25 | Jsr Corp | Thermosetting resin composition and cured article prepared therefrom |
| JP2002047421A (en) * | 2000-07-31 | 2002-02-12 | Toyo Ink Mfg Co Ltd | Antidegradant, thermoplastic resin composition, and molded article |
| WO2005118686A1 (en) | 2004-06-01 | 2005-12-15 | Kaneka Corporation | Soluble polyimide and optical compensation members made by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128599A (en) * | 1976-12-22 | 1978-12-05 | Celanese Corporation | Polyamides for extrusion applications |
| US6451890B1 (en) * | 1998-03-30 | 2002-09-17 | Nisshinbo Industries, Inc. | Polyamide resin composition |
| CN1938339A (en) * | 2004-03-26 | 2007-03-28 | 三井化学株式会社 | Novel resin modifier and polar group-containing polymer composition including same |
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| JP5507252B2 (en) | 2014-05-28 |
| WO2009054312A1 (en) | 2009-04-30 |
| CN101970536A (en) | 2011-02-09 |
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| KR101569222B1 (en) | 2015-11-13 |
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