JP2885872B2 - Aliphatic copolycarbonates and polyurethanes containing said units - Google Patents

Description

The present invention relates to a novel aliphatic copolycarbonate having excellent hydrolysis resistance, light resistance, oxidation deterioration resistance and heat resistance, and a polyurethane containing the same as a constituent unit. It is about.

[Conventional technology]

Conventionally, for example, polyester polyols and polyether polyols having a polymer terminal hydroxyl group have been used for soft segments used for thermoplastic elastomers such as polyurethane, urethane type, ester type and amide type (US Pat. No. 4,362,825, No. 4,73
No. 4,535, No. 4,129,715). Of these, polyester polyols represented by adipate are inferior in hydrolysis resistance.For example, polyurethanes using the same may cause cracks or the like on the surface in a relatively short period of time, or mold may grow on the surface, so that it is considerably difficult to use. Be restricted. On the other hand, a polyurethane using polyetherpoly-O has good hydrolysis resistance, but has a drawback of poor light resistance and oxidation-deterioration resistance. These disadvantages are attributable to the presence of an ester group and an ether group in the polymer chain, respectively. For polyester-based and polyamide-based thermoplastic elastomers, the demands for heat resistance, light resistance, hydrolysis resistance, mold resistance, oil resistance, and the like have been increasing in recent years. Had.

For example, aliphatic polyethers and polyetheresters having a methyldiacetoxysilane group at a terminal are used as sealing agents and the like.
No. 50-156599. However,
Since these compounds have an ether group in the main chain, they have a defect that they are inferior in light resistance, oxidation deterioration resistance and chlorine resistance. On the other hand, hydrolysis resistance, light resistance, oxidation deterioration resistance,
As a soft segment having excellent heat resistance and the like, polycarbonate polyol of 1,6-hexanediol is commercially available.This is because the carbonate bond in the polymer chain is extremely stable, and thus has the above-mentioned features. It is shown.

[Problems to be solved by the invention]

However, polyurethanes and polyester-based elastomers using 1,6-hexanediol polycarbonate polyols are said to have significantly poorer flexibility and elastic recovery than other polyols such as those using polyether polyols. Has disadvantages. Furthermore, as shown in a comparative example described later, when a polyurethane fiber is produced, spinning properties are lacking and spinning is difficult.

Various methods have been proposed to alleviate such problems. For example, U.S. Pat.No. 3,639,354 and European Patent No. 135,848 disclose a method of copolymerizing 1,6-hexanediol and a diol containing an ether group, and devising a method of slightly lowering the softening point of the polymer. Although the introduction of an ether group improves the flexibility when used in polyurethane, it deteriorates the light resistance and the oxidation-deterioration resistance. Further, in U.S. Pat.Nos. 4,103,070 and 4,101,529, a polycarbonate diol obtained by copolymerizing 1,6-hexanediol and 1,4-cyclohexanedimethanol was proposed, and the crystallinity of urethane using the same was proposed. It can be suppressed. However, since it contains a cyclo ring, even if the crystallinity is slightly deteriorated, the hardness due to the cyclo ring skeleton is imparted, and the improvement of the flexibility is hardly achieved. Further, Japanese Patent Application Laid-Open No. Sho 60-195117 proposes to impart flexibility by copolymerizing 3-methyl-1,5-pentanediol with 1,6-hexanediol or 1,9-nonanediol. . However, although having a side chain, the effect of breaking the crystallinity is great, but the light resistance and the oxidation deterioration resistance due to the side chain alkyl are weak. If it is desired to improve heat resistance, light resistance, oxidation deterioration resistance and the like in the publication, 3-methyl-1,5-
It is specified that pentanediol is used in an amount up to 50% by weight.

U.S. Pat. No. 4,013,702 and U.S. Pat. No. 4,105,641 describe the synthesis of a copolymerized copolycarbonate of 1,6-hexanediol and 1,4-butanediol. These all disclose a method for producing a copolycarbonate, and the properties thereof are not recorded,
As will be shown later in Comparative Example 6, the elastic recovery was not sufficient, and the spinning property was lacking when producing polyurethane fibers, making spinning difficult.

[Means for solving the problem]

Thus, an object of the present invention is to provide a resin group copolycarbonate and a polyurethane using the same, which can solve the above problems.

The present inventors have conducted intensive studies to achieve the above object, and as a result, the repeating unit is: Consisting of an aliphatic copolycarbonate having a ratio of A and B of 9: 1 to 1: 9 and a polyurethane or the like using the same as a constituent unit, has hydrolysis resistance, light resistance, chlorine resistance, oxidation deterioration resistance, Extremely good chemical stability such as heat resistance.In addition, when applied to polyurethane and other thermoplastic elastomers, it is more flexible than conventional 1,6-hexanediol-based polycarbonate polyols. It has been found that the fibers have excellent elastic recovery properties and can be spun in the production of polyurethane fibers, and the present invention has been accomplished.

 Hereinafter, the present invention will be described in detail.

The aliphatic copolycarbonate of the present invention comprises
hnell), Polymer Reviews
Vol. 9, pp. 9-20 (1964), containing 1,4-butanodiol and 1,5-pentanediol as main components and, in some cases, a small amount of an aliphatic polyol. Synthesized from aliphatic diols.

Repeating unit of main component in copolymer Is required to be 9: 1 to 1: 9 as the number of units. When the ratio of A and B is out of the range of 9: 1 to 1: 9, for example, in the case of polyurethane using the same, elastic recovery, flexibility and spinnability deteriorate, which is not preferable. Polyurethane using a copolycarbonate of a specific ratio of such repeating units A and B has both chemical stability and excellent elastic recovery, flexibility, and spinnability over urethane using conventional polycarbonate. The fact is that no one could imagine.

In the aliphatic copolycarbonate polyol used in the present invention, a small amount of a compound having two or more hydroxyl groups in one molecule other than 1,4-butanediol and 1,5-pentanediol impairs the effects of the present invention. Within the range
It may be used as a copolymer component. Depending on the case, for example, 1,4-butanediol and 1,5
-When pentanediol is polymerized in an equimolar amount,
As a component, 20% or less, preferably 15% or less can be used based on the total number of moles of 1,4-butanediol and 1,5-pentanediol.

The present invention also relates to compounds having three or more hydroxyl groups in one molecule in addition to 1,4-butanediol and 1,5-pentanediol, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol and the like. By using a small amount of the above, a polyfunctionalized polycarbonate is also included.

If too many compounds having three or more hydroxyl groups in one molecule are used, crosslinking occurs and gelation occurs. Therefore, the content may be set to 10% or less based on the total number of moles of the diol.

Repeating unit of the copolycarbonate of the present invention The concept of the ratio is as follows.

Copolycarbonate is a viscous liquid at room temperature and has an amorphous region that does not have a melting point as measured by DSC. Shows more preferable properties. When the copolycarbonate is a constituent unit of only A and B, the ratio of A and B is
Since amorphousness is exhibited in the range of 7.5: 2.5 to 2.5: 7.5, a composition in this range is a preferable region. When the third component is included as a copolymer component within the range that does not impair the effect in the structural units of A and B, the ratio of A and B spreads to the amorphous region up to the range of 9: 1 to 1: 9. .

The average molecular weight range of the copolycarbonate of the present invention,
Depends on application, but usually 300 to 50,000 in number average molecular weight
And preferably from 600 to 20,000.

The terminal group of the copolycarbonate of the present invention can be various groups depending on the application. For example, when used for polyurethane applications, the copolycarbonate end is
Substantially all must be hydroxyl groups. When used for polyester-based elastomers, carbonate-based elastomers, or polymer plasticizers, the terminal of the copolycarbonate may be a hydroxyl group, an alkyl carbonate group, or an aryl carbonate group, a carboxyl group, or an ester group. When used for polyamide elastomer applications, the copolycarbonate terminals must be substantially all carboxyl groups. Further, for use as a photosensitive resin or a coating agent or an optical material, it is necessary that substantially all of the terminals of the copolycarbonate are allyl groups or (meth) acryloyl groups. For use as a sealing agent, it is necessary that a silane group having a substituent, such as halogen, alkoxy, or acyloxy, which is reactive at room temperature, is present in at least one terminal of the copolycarbonate. Other, amino group, aminoalkyl group, glycidyl ether group, cyanoethyl group,
It is possible to have various functional groups such as an isocyanate group. Hereinafter, typical examples of various copolycarbonates and polyurethanes using them will be described in detail.

The copolycarbonate having a terminal hydroxyl group of the present invention is a novel polymer, and is represented by the general formula (1)
Is as follows.

(R ₂ is a glycol residue having a carbon number of 4,5 as a main component. N is a number of 2 to 200 on average, preferably a number of 4 to 100 on average.) Terminal of the present invention ( Copolycarbonates having (meth) acryloyl groups are novel copolymers and include (meth) acrylates and urethane (meth) acrylates of copolycarbonates having terminal hydroxyl groups.

The copolycarbonate urethane (meth) acrylate has a urethane bond in the molecular skeleton, includes a polycarbonate structure as a partial component of the molecular skeleton, and has a (meth) acryloyl group in the molecule. The synthesis method is known, for example, as follows.

1 mol of copolycarbonate polyol, 1.1 to 2 mol of diisocyanate compound and hydroxyalkyl (meth)
1.0 to 2 mol of acrylate can be obtained in the above order or by reacting these components at once. The copolycarbonate having a terminal hydroxyl group for obtaining (meth) acrylate and urethane (meth) acrylate is as described in detail above, and has a number average molecular weight of 500 to 20,000, preferably 1,000 to 10,000. Is good. The diisocyanate compound reacted with the copolycarbonate includes tolylene diisocyanate,
Diphenylmethane diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane diisocyanate, 1,6-hexane diisocyanate and the like having a molecular weight of usually about 170 to 1,000 are used. Further, as the hydroxyalkyl (meth) acrylate, those having a hydroxyalkyl group of about 2 to 4 carbon atoms such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are used.

The copolycarbonate having a terminal (meth) acryloyl group of the present invention is used as a main component of the photocurable resin composition.
Other polymerizable unsaturated compounds (for example, unsaturated polyester,
It is used together with unsaturated polyurethane, oligoester (meth) acrylate and the like and a photopolymerization initiator, and can be used as a raw material of a characteristic photocurable resin composition.

The copolycarbonate having a terminal allyl group of the present invention is a novel polymer, and a typical example is represented by the general formula (2):
It is as follows.

[R ₁ is hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. R ₂ is a glycol residue having 4,5 carbon atoms as a main component. n is a number ranging from 2 to 200 on average, preferably from 4 to 100 on average. ) The terminal allyl group is allyl, 2-chloroallyl, 2-bromoallyl, 2-methylallyl, 2-ethylallyl,
- propyl allyl, 2-but most commonly, and the like butyl allyl, allyl group R ₁ is hydrogen _{(CH 2 = CH-CH 2} -)
It is.

The copolycarbonate having a terminal allyl group of the present invention becomes a raw material of a sealant material which can be cured under environmental temperature conditions by introducing a silicon group by reacting with a hydrosilane as described later. In addition, it is also used as a raw material for optical device members such as lenses, fiber optic materials, and fiber optic devices.

The polycarbonate having a terminal carbonate group of the present invention is a novel polymer, and a typical example is represented by the following general formula (3).

(R ₂ is an aliphatic glycol residue having 4,5 carbon atoms as a main component, R ₃ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is an integer in the range of 2 to 200. The polyurethane of the present invention using a copolycarbonate having substantially all hydroxyl groups at the end is a novel polymer, which comprises a copolycarbonate polyol and a polyisocyanate and, if necessary, an active hydrogen atom capable of reacting with the polyisocyanate. It is synthesized from a chain extender having at least two.

 The details of the new polyurethane will be described below.

The range of the average molecular weight of the copolycarbonate polyol used in the polyurethane of the present invention varies depending on the application, but is usually 300 to 50,000 in number average molecular weight, preferably 600 to 20,000, more preferably 700 to 6,000. You. Details of the other copolycarbonate polyols are as described above.

Examples of the polyisocyanate used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and a mixture thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), and naphthalene-1. , 5-Diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenylenediisocyanate (TOD
I), known aromatic diisocyanates such as crude TDI, polymethylene polyphenylisocyanate, crude MDI and the like, and known aromatic alicyclic diisocyanates such as xylylene diisocyanate (XDI) and phenylene diisocyanate;
4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMD
Known aliphatic diisocyanates such as I), isophorone diisocyanate (IPDI) and cyclohexane diisocyanate (hydrogenated XDI), and isocyanurate-modified, carbodiimidated and biuret-modified products of these isocyanates.

In the present invention, suitable chain extenders used as needed include those commonly used in the polyurethane industry. The latest polyurethane application technology supervised by Keiji Iwata CMC 1985, pages 25 to 27, including well-known water, low molecular polyol, polyamine and the like.

A known polyol may be used in combination with the copolycarbonate polyol used in the present invention, depending on the use of the polyurethane, as long as the effects of the present invention are not impaired.
As the known polyol, there are known polyols such as polyester and polyether polycarbonate described in Yoshio Imai, Polyurethane Foam Polymer Publishing Association, pp. 12-23, 1987.

As a method for producing the polyurethane, a technique of a urethane reaction known in the polyurethane industry is used. For example, the polyol and the organic polyisocyanate are kept at room temperature to about
The reaction at 200 ° C. produces an NCO-terminated polyurethane prepolymer. These can be used as a one-pack type solventless adhesive or sealant which is cured by reacting with moisture in the air. This prepolymer and another polyol,
A known cross-linking agent (a low-molecular compound having two or more active hydrogen atoms capable of reacting with isocyanate) can be used in combination with a two-pack type casting material in combination.

In addition, a cross-linked or thermoplastic polyurethane can be produced by using a method such as a one-shot method, a prepolymer method, or a RIM method using the polyol, the polyisocyanate and, if necessary, a chain extender.

In these productions, known polymerization catalysts represented by organic metal salts such as tertiary amines, tin, and titanium (e.g.,
Keiji Iwata "Polyurethane resin" Published by Nikkan Kogyo Shimbun 23
, Page 32 (1969)].
These reactions may be carried out using a solvent, and preferred solvents include dimethylformamide, diethylformamide, dimethylsulfoxide, dimethylacetamide, tetrahydrofuran, methylisobutylketone, dioxane, cyclohexanone, benzene, toluene, and ethylcellosolve. is there.

In the production of the polyurethane of the present invention, a compound containing only one active hydrogen that reacts with an isocyanate group, for example, monohydric alcohols such as ethyl alcohol and propyl alcohol and secondary amines such as diethylamine and di-n-propylamine Etc. may be used as a terminal terminator.

Next, several uses of the polyurethane obtained by the present invention will be described.

(1) Substantially linear thermoplastic polyurethane pellets are formed, heated and melted, and molded articles such as elastomer films and sheets, hoses, tubes, rolls, and gears are formed by injection molding, extrusion molding, calendering, or the like. To manufacture.

(2) The carbonate polyol is reacted with an organic polyisocyanate to form a prepolymer having a molecular terminal isocyanate group, and is cured by moisture, or is cast using a chain extender of diol or diamine, and is used as a casting material, a paint, a sealant, or an adhesive. Used for agent use.

(3) In the above (1) and (2), a polyurethane solution obtained by dissolving a polyurethane raw material in a solvent is used as a coating agent for synthetic leather, artificial leather, fiber, nonwoven fabric, or the like, or magnetic powder, conductive powder, pigment / dye. Is used as a magnetic agent, electromagnetic shielding paint, gravure ink and the like.

(4) A thermosetting foam product in which various additives such as a freon-based foaming agent are blended with the polycarbonate polyol, and an organic polyisocyanate or a prepolymer having a molecular terminal isocyanate group is added thereto, followed by high-speed stirring and foaming. To manufacture.

(5) The isocyanate prepolymer having a molecular end is dissolved in a solvent, and a known diamine or diol chain extender or the like is added thereto to prepare a stable spinning stock solution. From this stock solution, a wet method, a dry method or an extrusion method is used. Manufacture elastic yarn.

More specifically, the polyurethane of the present invention is excellent not only in abrasion resistance, impact resistance, hydrolysis resistance, oxidation deterioration resistance, light resistance, low temperature flexibility and flexibility but also in elasticity. It is a polyurethane which is remarkably excellent in resilience, and can cover all of a wide range of applications where a conventional polyurethane has been used. For example, open-cell foam (cushion material), closed-cell foam (microcellular shoe sole), film, sheet, tube, hose, vibration-proof material, packing material, adhesive, van binder, sealant, from rigid to semi-rigid to soft It is useful for waterproofing materials, flooring materials, casting materials, paints, elastic fibers and the like.

〔Example〕

Hereinafter, the present invention will be described in more detail by examples,
The present invention is not limited in any way by these examples.

Copolycarbonate having hydroxyl group terminal The hydroxyl value in the examples was measured by an acetylation method.
The terminal of the polymer in Examples and Comparative Examples was ¹³ C-NMR (270 MHz
From the measurement in z), substantially all were hydroxyl groups. Further, the acid value in the polymer was measured by titration with KOH, and it was found that the values of all polymers in Examples and Comparative Examples were 0.01 or less. Therefore, the number average molecular weight of the obtained polymer is determined by the following equation.

Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.11) Examples 1-4 After stirring, a polyhydric alcohol as shown in Table 1 was added to a reactor equipped with a thermometer and a distillation tube. At 70-80 <0> C, metallic sodium was added under stirring. After the sodium had completely reacted, the amount of diethyl carbonate shown in Table 1 was introduced. When the reaction temperature was raised to 95-100 ° C. at normal pressure, ethanol began to distill. The temperature was gradually raised to 160 ° C. for the time shown in Table 1. During this time, ethanol containing about 10% diethyl carbonate was distilled off. Thereafter, the pressure in the reactor was further reduced to 10 mmHg or less, and the reaction was carried out at 200 ° C. with vigorous stirring at 200 ° C. while extracting ethanol. The resulting polymer was dissolved in dichloromethane after cooling, neutralized with a dilute acid, washed repeatedly with water several times, dehydrated with anhydrous sodium sulfate, distilled off the solvent, and further removed by 2 to 3 mmH.
g, dried at 140 ° C. for several hours. Table 1 shows the properties of the obtained copolycarbonate diol.

Example 5 [Copolycarbonate urethane acrylate] In a 3 l four-necked flask equipped with a stirrer, a condenser and a thermometer, the copolycarbonate obtained in Example 1 (OH value: 62.
4 mg KOH / g) 1 mol, tolylene diisocyanate 2 mol,
2 mol of 2-hydroxyethyl acrylate and 200 ppm of dibutyltin urarate were charged and reacted at 60 to 70 ° C. to obtain a copolycarbonate urethane acrylate as a 2-hydroxyethyl acrylate solution. This reaction is based on the infrared absorption spectrum of 2,270 cm ⁻¹ of isocyanate group.
Until the characteristic absorption band disappeared.

Example 6 [copolycarbonate urethane methacrylate] The copolycarbonate obtained in Example 1 (OH value: 62.4 mgKOH
/ g) 1 mol, 2.0 mol of hexamethylene diisocyanate and 20 ppm of dibutyltin laurate were added and reacted at 80 ° C. for 3 hours to obtain a urethane polymer having a terminal isocyanate. Next, 1 mol of 2-hydroxypropyl methacrylate was added and reacted for 3 hours until the characteristic absorption band of isocyanate disappeared by infrared absorption spectrum, to obtain a copolycarbonate urethane methacrylate as a 2-hydroxypropyl methacrylate solution.

Example 7 [Copolycarbonate having an allyl group terminal] 162 g of copolycarbonate obtained in Example 1 and 36 of toluene
A mixture of 0 g and 11.5 g of pyridine was cooled to 10 ° C., and 40 g of acryl chloroformate was gradually added with stirring. After warming the solution to 25 ° C., it was filtered to remove pyridine hydrochloride. After washing the filtrate several times with water, the solvent was distilled off to obtain a copolycarbonate having an allyl end group.

Example 8 [Copolycarbonate having alkyl group terminal] (1) Synthesis of bisalkyl carbonate 299 g (3.32 mol) of 1,4-butanediol, 5,976 g (66.4 mol) of dimethyl carbonate, dibutyldimethoxytin
0.2 g (0.00067 mol) was put in an autoclave and reacted at 220 ° C. for 3 hours. After the completion of the reaction, dimethyl carbonate was removed by distillation under reduced pressure, and the product, bismethyl carbonate of 1,4-butanediol, was obtained in a yield of 98.0%.

Further, bismethyl carbonate of 1,5-pentanediol was obtained in the same manner as described above.

(2) Polymerization of bisalkyl carbonate 1,4-butanediol and bismethyl carbonate of 1,5-pentanediol were each 176.3 g (0.86 mol),
189.2 g (0.8 mol) was put into a reaction vessel equipped with a stirrer, a thermometer and a distilling tube, and 2 g (0.008 mol) of dibutyltin oxide was further added. The pressure was gradually reduced from normal pressure at 220 ° C. under an argon atmosphere. Then, condensation polymerization was performed while removing dimethyl carbonate for 5 hours so that the pressure was finally reduced to 5 mmHg. The resulting polymer was a transparent, amorphous bismethyl copolycarbonate. The molecular weight was 14,000 by GPC.

Polyurethane using hydroxyl group-terminated copolycarbonate Intrinsic viscosity [η] of polyurethane in Examples and Comparative Examples is
It was in the range of 0.8 to 1.2.

The hydrolysis resistance of the polyurethane in the examples is 100μ.
Was treated in hot water at 100 ° C. for 12 hours, and the film was evaluated by the retention of the average molecular weight measured by GPC.

The light resistance was evaluated by the tensile breaking strength retention after irradiating the above film with a carbon arc ultraviolet ray of 380 nm by a Ford meter for 25 hours.

Oxidation degradation resistance was evaluated by the thermal decomposition onset temperature by TGA (heating in air at 10 ° C./min).

As for elastic recovery, after stretching a 100μ polyurethane film at room temperature by 300% in about 90 seconds, holding it for about 90 seconds, suddenly shrinking, measuring the length, and evaluating its permanent elongation .

The intrinsic viscosity was determined by preparing a polyurethane solution prepared by dissolving 0.02 g, 0.05 g, and 0.1 g of polyurethane in 100 ml of a dimethylacetamide solution, measuring the reduced viscosity at 30 ° C., and extrapolating the polyurethane concentration to zero.

Examples 9 to 11 Aliphatic copolycarbonate diol A was prepared in the same manner as in Example 1 except that 1,4-butanediol and 1,5-pentanediol were used in the amounts shown in Table 2 as diols.
To PC (abbreviated as PC-A to PC-C). Each OH value was as shown in Table 2.

Comparative Example 1 A polycarbonate diol was obtained in the same manner as in Example 1 except that 944 g (8.0 mol) of 1,6-hexanediol was used. The OH value was 55.0. (Abbreviation PC-D) Comparative Example 2 Copolycarbonate diol-L (472 parts (4.0 mol) and 1,4-butanediol 360 parts (4.0 mol) was used in the same manner as in Example 1. PC-E). The OH value was 58.1.

Examples 12 to 15 and Comparative Examples 3 to 6 PC-A to PC-D shown in Examples, polytetramethylene glycol synthesized by Asahi Kasei Corporation (OH value 59.6, PT
MG), polytetramethylene adipate (manufactured by Dic, OH value: 58.3, abbreviated as PTA), any one of the polyols (dehydrated under reduced pressure and heated) in toluene 4 times the weight of the polyol / MIBK (1/1 wt / wt) and heated to 100 ° C. (charged amounts are shown in Table 3).

Next, a predetermined amount of hexamethylene diisocyanate (HD
I) and diphenylmethane-4,4'-diisocyanate (abbreviated as MDI) in the form of toluene / MIBK (1/1 wt / w
t), and added to the above-mentioned polyol solution and mixed (the charged weight is shown in Table 3).

Next, 10% by weight of dibutyltin laurate in toluene / MIB
A K (1/1 wt / wt) solution was added so as to be 100 ppm based on the solid matter in the solution, and the mixture was stirred at 100 ° C for 1 hour to obtain a prepolymer.

Next, a predetermined amount of a chain extender of one of 1,4-butanediol and ethylene glycol and toluene / MIBK (1/1 wt / w
t) (the amount of the solvent was adjusted so that the solid content in the solution was 25% by weight), and the mixture was stirred vigorously at 100 ° C. for 1 hour (the charged amount is shown in Table 3). Was obtained.

Next, the solvent was removed from this polymer solution under reduced pressure to obtain a polyurethane. Table 3 shows the evaluation results of various performances of these polyurethanes.

Example 16 and Comparative Examples 7 to 10 Two moles each of PC-A, PC-D, PC-E, PTMG, polyhexamethylene neopentylene adipate (manufactured by Bayer, OH value 56.0, abbreviated as PHNA) and diphenylmethane- 4,4'-
4 mol of diisocyanate was reacted under stirring in a nitrogen stream at 80 ° C. without a solvent for 4 hours to produce an isocyanate-terminated prepolymer, which was then cooled to room temperature and dissolved by adding sufficiently dehydrated dimethylacetamide. A dimethylacetamide solution in which 2 mol of ethylenediamine was dissolved was added to the solution at once, and the mixture was stirred at room temperature for 30 minutes to obtain five 30% by weight polyurethane solutions. A part of the polyurethane solution was cast to obtain a 100 μm film, and data on hydrolysis resistance, light resistance, oxidation deterioration resistance, and elastic recovery were obtained. The results are shown in Table 4.

In addition, most of the polyurethane solution was spun by a small spinning device to obtain polyurethane fibers. The results are shown in Table 4.

[Effects of the Invention] The aliphatic copolycarbonate of the present invention is liquid at room temperature and is easy to handle, and the polyurethane using the aliphatic copolycarbonate of the present invention is extremely excellent in any property and has high chemical stability. It is an unprecedented high-performance polyurethane that has both properties and excellent rubber-like properties.

Claims (4)

(57) [Claims] (1) As a repeating unit, Wherein the ratio of A and B is 9: 1 to 1: 9, and the number average molecular weight is 30.
0-50,000 copolycarbonate. 2. The copolycarbonate has an A / B of 75/25 to 25/7.
The copolycarbonate according to claim 1, wherein the number is 5. 3. The terminal of the copolycarbonate is hydroxyl group, acryloyl group, methacryloyl group, allyl group,
The copolycarbonate according to claim 1 or 2, wherein the copolycarbonate is selected from an alkyl carbonate group and an aryl carbonate group. 4. The repeating unit Wherein the ratio of A and B is 9: 1 to 1: 9, and the number average molecular weight is 30.
Polyurethane containing from 0 to 50,000 copolycarbonates as constituent units.