JPH047327A - Aliphatic copolycarbonate and polyurethane containing the same as structural unit - Google Patents

Abstract

PURPOSE:To prepare the title polyurethane having improved resistances to hydrolysis, light, chlorine, degradation by oxidation, and heat by incorporating a specific copolycarbonate as a structural unit into the polyurethane. CONSTITUTION:1,4-Butanediol, 1,5-pentanediol, and, if necessary, another compd. having at least two hydroxyl groups in the molecule (e.g. trimethylolethane) are allowed react with diethyl carbonate to give an aliph. copolycarbonate polyol contg. repeating units of formulas I and II in a ratio of formula I/II of (9:1) to (1:9) and having an average mol.wt. of 300-50000. One mol of the copolycarbonate polyol, 1.1-2mol of diisocyanate having a mol.wt. of 170-1000, and a hydroxyalkyl (meth)acrylate are made to react to give a polyurethane contg., as a structural unit, an aliph. copolycarbonate contg. repeating units of formulas I and II.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel aliphatic copolycarbonate having excellent hydrolysis resistance, light resistance, oxidative deterioration resistance, and heat resistance, and a polyurethane containing this as a structural unit. It is related to.

[Conventional technology]

Conventionally, polyester polyols and polyether polyols in which the polymer ends have hydroxyl groups have been used for soft segments used in thermoplastic elastomers such as polyurethane, urethane-based, ester-based, and amide-based elastomers (U.S. Patent No. No. 4,362,825,
No. 4,374,535, Specification No. 4,129,715, etc.). Among these, polyester polyols such as adipate have poor hydrolysis resistance. For example, polyurethanes made using these polyols tend to develop cracks or mold on the surface in a relatively short period of time, making them difficult to use. quite limited. On the other hand, polyurethane using polyether polyol has good hydrolysis resistance, but has poor light resistance and
It has the disadvantage of poor oxidation resistance.

These drawbacks are due to the presence of ester groups and ether groups in the polymer chain, respectively. In recent years, thermoplastic elastomers such as polyester and polyamide have
The requirements for heat resistance, light resistance, hydrolysis resistance, mold resistance, oil resistance, etc. have become more sophisticated, and they have the same problems as those for polyurethane.

In addition, for example, aliphatic polyethers and polyether esters having a methyldiacetoxysilane group at the end are used as sealants.
It is disclosed in JP 0-156599 and the like. However, since these compounds have an ether group in their main chain, they have the drawback of being inferior in light resistance, oxidative deterioration resistance, and chlorine resistance.

On the other hand, 1,6-hexanediol polycarbonate polyol is commercially available as a soft segment with excellent hydrolysis resistance, light resistance, oxidation resistance, heat resistance, etc., but this is because the carbonate bonds in the polymer chain are chemically bonded. Since it is extremely stable, it exhibits the above-mentioned features.

[Problem to be solved by the invention]

However, polyurethane and polyester elastomers using polycarbonate polyols such as 1,6-hexanediol have the drawback of significantly poor flexibility and elastic recovery compared to those using other polyols, such as polyether polyols. have. Furthermore,
As seen in the comparative examples shown later, when producing polyurethane fibers, they lack spinnability and are difficult to spin.

Various methods have been proposed to alleviate these problems. For example, U.S. Patent No. 3.639,3
1 in Specification No. 54 and European Patent No. 135,848.
．． A method of copolymerizing 6-hexanediol and a diol containing an ether group has been disclosed, and efforts have been made to slightly lower the softening point of the polymer. However, the light resistance and oxidative deterioration resistance deteriorate. Also, U.S. Patent Nos. 4,103,070 and 4,1
No. 01,529, L6-hexanediol and 1
．． They proposed a polycarbonate diol copolymerized with 4-cyclohexane dimetatool, and said that it is possible to suppress the crystallinity of urethane using it. However, since it contains a cyclo ring, even though the crystallinity is slightly degraded, the hardness due to the cyclo ring skeleton is imparted, and the flexibility is not significantly improved. Furthermore, JP-A-60-1
No. 95117 proposes imparting flexibility by copolymerizing 3-methyl-1,5-bentanediol and 1,6-hexanediol or 1°9-nonanediol. However, although having a side chain has a great effect on disrupting crystallinity, the light resistance and oxidative deterioration resistance are weak due to the side chain alkyl. The publication also mentions heat resistance, light resistance,
If you want to improve the oxidative deterioration resistance etc., 3-methyl-
It is specified that 1°5-bentanediol is used in an amount of up to 50% by weight.

Also, U.S. Patent No. 4,013,702 and U.S. Patent No. 4.
No. 105,641 describes the synthesis of a copolycarbonate of 1,6-hexanediol and 1,4-butanediol. All of these disclose methods for producing copolycarbonate, but do not record its properties; however, as will be shown later in Comparative Example 6, elastic recovery is insufficient, and when producing polyurethane fibers. It lacked spinnability and was difficult to spin.

[Means to solve the problem]

Therefore, an object of the present invention is to provide an aliphatic copolycarbonate that can solve the above problems and a polyurethane using the same.

As a result of extensive research to achieve the above object, the present inventors found that the repeating unit is A: + OA: CHzh-0-C→ and B: (
-0+CHz)r Consisting of O-C→-I, A, l! :Aliphatic copolycarbonate with a B ratio of 9:1 to 1:9 and polyurethane using it as a constituent unit have excellent properties such as hydrolysis resistance, light resistance, chlorine resistance, oxidative deterioration resistance, and heat resistance. It has very good chemical stability, and in addition, when applied to polyurethane and other thermoplastic elastomers, it has greater flexibility and elastic recovery than traditional 1,6-hexanediol-based polycarbonate polyols. It has been discovered that this method is excellent, and that it can also be spun in the production of polyurethane fibers, leading to the present invention.

The present invention will be explained in detail below.

The aliphatic copolycarbonate of the present invention is manufactured by Cineel (Sc
Polyme Reviews
rReviews) Volume 9, pages 9-20 (1964)
It is synthesized from aliphatic diols containing 1,4-butanediol and 1,5-bentanediol as main components and, in some cases, a small amount of aliphatic polyol, by various methods described in .

The ratio of the main component repeating 7 units A:+0+CH2h-0-C and B:+0+CH2h-0-C+ in the copolymer needs to be 9:1 to 1:9 in terms of the number of units. If 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 this, elastic recovery properties, flexibility, and stringiness deteriorate, which is not preferable. Repeat 7 units A like this.

The fact that polyurethane made with a specific proportion of copolycarbonate (B) has both chemical stability and superior elastic recovery, flexibility, and stringability than urethane made with conventional polycarbonate has been well-known to many people. This was something I could never have imagined.

In the aliphatic copolycarbonate polyol used in the present invention, in addition to 1,4-butanediol and 1゜5-bentanediol, a small amount of a compound having two or more hydroxyl groups in one molecule may impair the effects of the present invention. It may be used as a copolymer component within a certain range. Although it varies depending on the case, for example, when polymerizing equimolar amounts of 1,4-butanediol and 1,5-bentanediol, 1,4-butanediol and 1,5-bentanediol are used as the third component.
It can be used in an amount of 20% or less, preferably 15% or less, based on the total number of moles of 5-bentanediol.

In addition to 1,4-butanediol and 1.5-bentanediol, the present invention also includes compounds having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, and pentaerythritol. Polyfunctionalized polycarbonates are also included in small amounts.

If too many compounds with three or more hydroxyl groups in one molecule are used, crosslinking will occur and gelation will occur.
It may be kept at 10% or less based on the total number of moles of diol.

Repeating unit A of the copolycarbonate of the present invention: +
O+ CHz)rOC÷ and B:÷0(CH, 斥O−
The concept of the ratio of C→- is as follows.

Copolycarbonate is a viscous liquid at room temperature, and has a melting point of less than 7 as determined by DSC measurement. When used in polyurethane, for example, copolycarbonate has excellent elastic recovery, flexibility, and stringiness. It shows more preferable properties in terms of. If the copolycarbonate has only A and B as constituent units, it exhibits poor quality when the ratio of A and B is in the range of 7.5:2.5 to 2.5 to 71.5, so the composition within this range is This is a preferred area. When a third component is included as a copolymer component in the structural units of A and B to the extent that it does not impair the effect, A and B
The amorphous region expands to a range where the ratio is from 9:1 to 1:9.

The range of the average molecular weight of the copolycarbonate of the present invention varies depending on the use, but it usually ranges from 300 to 50 in terms of number average molecular weight.
, 000, preferably 600 to 20,000.

The terminal groups of the copolycarbonate of the present invention can be made into various groups depending on the use. For example, when used in polyurethane applications, the copolycarbonate ends must be substantially all hydroxyl groups.

When used for polyester elastomers, carbonate elastomers, or polymer plasticizers, the copolycarbonate terminals are hydroxyl groups, alkyl carbonate groups, aryl carbonate groups, carboxyl groups,
Alternatively, it may be an ester group. When used in polyamide elastomer applications, substantially all of the copolycarbonate terminals must be carboxyl groups.

Further, for use in photosensitive resins, coating agents, and optical materials, it is necessary that substantially all of the terminal ends of the copolycarbonate be allyl groups or (meth)acryloyl groups.

Further, for use as a sealant, it is necessary that a silane group having a substituent such as halogen, alkokene, or acyloxy, which is reactive at room temperature, be present at at least one terminal of the copolycarbonate. In addition, it is possible to provide various functional groups such as an amino group, an aminoalkyl group, a glycidyl ether group, a sia group, an ethyl group, and an isocyanate group. Representative examples of various copolycarbonates and polyurethanes using them will be individually described in detail below.

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

II HO+ RzOCO+-RzOH~---------(1
) (R2 is a glycol residue containing 4,5 carbon atoms as a main component. n is a number on average of 2 to 200, preferably a number of 4 to 100 on average.) Terminal of the present invention ( Meta)
Copolycarbonates with acryloyl groups are new copolymers, consisting of (meth)acrylates and urethane (meth)acrylates of copolycarbonates with terminal hydroxyl groups.
Contains acrylates.

What is copolycarbonate urethane (meth)acrylate?
It has a urethane bond in its molecular skeleton, a polycarbonate structure as a part of the molecular skeleton, and a (meth)acryloyl group in this molecule, and its synthesis method is known, for example It is as follows.

1 mole of copolycarbonate polyol, 1.1 to 2 moles of diisocyanate compound, and hydroxyalkyl (meth)
It can be obtained by reacting 1.0 to 2 moles of acrylate 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 above in detail, and has a number average molecular weight of 500 to 20,000, preferably 1,000 to 10
,000 is preferable. Further, as the diisocyanate compound to be reacted with this copolycarbonate, tolylene diisocyanate, diphenylmethane diisonanate, naphthalene diisocyanate, isophorone diisocyanate, bis(isocya X-tomethyl)cyclohexane, dicyclohexylmethane diisocyanate, 1.6
-Molecular weight of hexane diisocyanate etc. is usually 170
~1,000 is used. Furthermore, as hydroxyalkyl (meth)acrylate,
Those having a hydroxyalkyl group having 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 can be used as a main component of a photocurable resin composition in combination with other polymerizable unsaturated compounds (for example, unsaturated polyester, unsaturated polyurethane, oligoester (meth)acrylate). etc.) and a photopolymerization initiator, and can be used as a raw material for a unique photocurable resin composition.

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

II II IICHHz=
C-C) I2-OCO+RzOCO±-ii R20C
OCH2-C-C)12CR, is hydrogen, halogen or 1
An alkyl group having ~4 carbon atoms. R2 is a glycol residue having 45 carbon atoms as a main component. n is a number ranging from 2 to 200 on average, preferably; < is a number ranging from 4 to 100 on average. ) The terminal allyl group is allyl, 2-chloroallyl, 2-bromoallyl, 2-methylallyl, 2-ethylallyl, 2-
Allyl groups include propyl allyl, 2-butyl allyl, etc., but most commonly, allyl groups where R1 is hydrogen (CHz=CH-C
Hz-).

The copolycarbonate having a terminal allyl group of the present invention is
As described below, silicon groups are introduced by reacting with hydrosilanes, and it becomes a raw material for sealant materials that can be cured under ambient temperature conditions.

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 thereof is represented by the general formula (3) as follows.

R30CO-f-RZOCO-+-1-R3(3)(R
2 is an aliphatic glycol residue mainly having 4.5 carbon atoms, R3 is an alkyl group having 1 to 10 carbon atoms or 6 to 1 carbon atoms
0 aryl group, n is an integer in the range of 2-200. ) The polyurethane of the present invention using a copolycarbonate having substantially all terminals with hydroxyl groups is a new polymer, in which a copolycarbonate polyol and a polyisocyanate, and if necessary at least an active hydrogen atom capable of reacting with the polyisocyanate, are used. It is synthesized from two chain extenders.

Details of the new polyurethane will be described below.

The average molecular weight range of the copolycarbonate polyol used in the polyurethane of the present invention varies depending on the use, but
The number average molecular weight is usually 300 to 50.000, preferably 600 to 20.000, and more preferably Huff 0 to 50.000.
6,000 are used. Details of other copolycarbonate polyols are as described above.

Examples of the polyisocyanate used in the present invention include 2,4-trilylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), and diphenylmethane-4,4'-diisocyanate (MDI).
, naphthalene-R5-diisocyanate (NDT), 3
．． Known aromatic diisocyanates such as 3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), crude TDI, polymethylene polyphenylisocyanate, and crude MDI, and xylylene diisocyanate (XD
I), known aromatic alicyclic diisocyanates such as phenylene diisocyanate, 4.4' methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI) ) and other known aliphatic diisocyanates, and isocyanurate-modified products, carbodiimidized products, biuret-modified products of these isocyanates, and the like.

Further, in the present invention, suitable chain extenders used as necessary include chain extenders commonly used in the polyurethane industry. The known water described in the latest polyurethane application technology CMCl985, pages 25-27, supervised by Keiji Iwata,
Includes low molecular polyols, polyamines, etc.

Along with the copolycarbonate polyol used in the present invention, a known polyol may be used in combination, depending on the intended use of the polyurethane, within a range that does not impair the effects of the present invention. As known polyols, there are known polyols such as polyesters and polyether polycarbonates described in Yoshio Imai, Polyurethane Foam, Kobunshi Publishing Co., Ltd., 1987, pages 12-23.

As the method 7 for producing polyurethane, a urethanization reaction technique known in the polyurethane industry is used. For example, an NGO-terminated polyurethane prepolymer is produced by reacting the polyol with an organic polyisocyanate at room temperature to about 200°C. These can be used in one-component solvent-free adhesives and sealants that cure by reacting with moisture in the air. This prepolymer, another polyol, and a known crosslinking agent (a low-molecular compound having two or more active hydrogen atoms that can react with isocyanate) can be combined to be used in a two-component casting material or the like.

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

In the production of these, known polymerization catalysts such as tertiary amines and organic metal salts such as tin and titanium are used [for example, "Polyurethane Resins" by Keiji Iwata, published by Nikkan Kogyo Shimbun, 23.
-32 pages (1969)] can also be used. Further, these reactions may be carried out using a solvent, and preferred solvents include dimethylformamide, diethylformamide, dimethyl sulfoxide, dimethylacetamide, tetrahydrofuran, methyl isobutyl ketone,
Dioxane, cyclohexanone, Hensen, toluene,
Examples include ethyl cellosolve.

In addition, in producing 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, secondary amines such as diethylamine and diropropylamine, etc. may be used as the terminal capping agent 7.

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

(1) Molded products such as elastomer films, sheets, hoses, tubes, rolls, gears, etc. by making substantially linear thermoplastic polyurethane pellets, heating and melting them, and using methods such as injection molding, extrusion molding, and calendering. Manufacture.

(2) The carbonate polyol and organic polyisocyanate are reacted to produce a prepolymer having isocyanate groups at the molecular terminals, which can be cured with moisture or used as a casting material, paint, sealant, adhesive, etc. using a diol or diamine chain extender. Used for agent purposes.

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

(4) A thermosetting foam product is obtained by blending various additives such as a freon foaming agent with the polycarbonate polyol, adding an organic polyisocyanate or a prepolymer having a molecular terminal isocyanate group, and foaming the mixture by stirring at high speed. Manufacture.

(5) Dissolve the molecular-terminated isocyanate prepolymer in a solvent, add a known diamine or diol chain extender, etc. to prepare a stable spinning stock solution, and use this stock solution by wet method, dry method, or extrusion method. Manufacture elastic yarn.

More specifically, the polyurethane of the present invention not only has excellent abrasion resistance, impact resistance, hydrolysis resistance, oxidative deterioration resistance, light resistance, low temperature flexibility, and flexibility.
It is a polyurethane with extremely excellent elastic recovery properties, and can cover a wide range of applications for which conventional polyurethanes have been used. For example, open cell foam (cushion material) ranging from hard to semi-hard to soft, closed cell foam (microcellular shoe sole), film, sheet, tube, hose, vibration isolating material, banking material, adhesive material,
Useful for binders, sealants, waterproof materials, flooring materials, casting materials, paints, elastic fibers, etc.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The hydroxyl value in the hydroxyl-containing copolycarbonate examples was measured by the acetylation method. Example,
The terminal of the polymer in the comparative example was determined by "C-NMR (270MH
According to the measurement of z), substantially all of them were hydroxyl groups. Furthermore, the acid value in the polymer was measured by titration with KOH, and all the polymers of Examples and Comparative Examples were 0.
It was 01 or less. Therefore, the number average molecular weight of the obtained polymer is determined by the following formula.

Number average molecular weight -2/(00 valent Xl0 - 3156.11)
Examples 1 to 4 After stirring, polyhydric alcohols as shown in Table 1 were added to a reactor equipped with a thermometer and a fractionating tube, and metallic sodium was added at 70 to 80°C under stirring.

After the sodium had completely reacted, diethyl carbonate was introduced in the amount shown in Table 1. The reaction temperature is 95% at normal pressure.
When the temperature was raised to ~100°C, ethanol began to distill out. Gradually raise the temperature to 160°C for the time shown in Table 1.
And so. During this time, ethanol containing about 10% diethyl carbonate was distilled out.

Thereafter, the pressure in the reactor was further lowered to 1101 H or less, and the reaction was carried out at 200°C with strong stirring for the time shown in Table 1 while extracting ethanol. After cooling, the produced polymer was dissolved in dichloromethane, neutralized with dilute acid, washed with water several times, dehydrated with anhydrous sodium sulfate, and the solvent was removed by distillation. Let dry for several hours. Table 1 shows the properties of the copolycarbonate diol obtained.

Example 5 [Copolycarbonate urethane acrylate] The copolycarbonate obtained in Example 1 (OH value:
62.4■KOH/g) 1 mol, tolylene diisocyanate 2 mol, 2-hydroxyethyl acrylate 2
mol and dibutyltin urarate 200ppm,
The reaction was carried out at 60-70°C to obtain copolycarbonate urethane acrylate as a 2-hydroxyethyl acrylate solution. This reaction was carried out until the characteristic absorption band of 2,270 Cl0-' of the isocyanate group disappeared from the infrared absorption spectrum.

Example 6 [Copolycarbonate urethane methacrylate] Copolycarbonate obtained in Example 1) (OH value = 62.4
■KOH/g) 1 mol, hexamethylene diisocyanate 2.0 mol and diptyltin laurate 2Qppn+
was added and reacted at 80°C for 3 hours to obtain a urethane polymer with isocyanate at both terminals. Next, 1 mol of 2-hydroxypropyl methacrylate was added and the mixture was heated for 3 hours until the characteristic absorption band of isocyanate disappeared from the infrared absorption spectrum.
After reacting for a period of time, copolycarbonate urethane methacrylate was obtained as a 2-hydroxypropyl methacrylate solution.

Example 7 [Allyl group-terminated copolycarbonate] A mixture of 162 g of the copolycarbonate obtained in Example 1, 360 g of toluene, and 11.5 g of pyridine was cooled to 10°C, and 40 g of acrylic 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 removed by distillation to obtain a copolycarbonate with allyl end groups.

Example 8 [Copolycarbonate with alkyl group terminals] (1) 299 g (3.32 mol) of 1,4-butanediol containing bisalkyl carbonate and 5,976 g (66.4 mol) of dimethyl carbonate,
0.2 g (0,00067 mol) of diptylddimethoxytin was placed in an autoclave and reacted at 220°C for 3 hours.

After the reaction was completed, dimethyl carbonate was removed by distillation under reduced pressure, and the product bismethyl carbonate of 1,4-butanediol was obtained with a yield of 98.0%.

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

(2) 176.3 g (0.86 mol) and 189.2 g (0.8 mol) of bis-alkyl carbonate 1,4-butanediol and 1.5-bentanediol, respectively, in a stirrer; The mixture was placed in a reaction group equipped with a thermometer and a distillation tube, and 2 g (0,008 mol) of dibutyltin oxide was added thereto, and the pressure was gradually reduced from normal pressure at a temperature of 220°C under an argon atmosphere.
Finally, condensation polymerization was carried out for 5 hours while removing dimethyl carbonate so that the pressure was reduced to 5 mmHg. The resulting polymer was a clear, amorphous bismethyl copolycarbonate. The molecular weight was 14,000 by GPC.

Hydroxyl acupoint 1 carbony example,
The intrinsic viscosity [η] of the polyurethane in the comparative example is 0.8 to 1
．． It was within the range of 2.

In addition, the hydrolysis resistance of polyurethane in the examples is 100μ
A polyurethane film having a thickness of 100° C. was treated in hot water at 100° C. for 12 hours, and the film was evaluated based on the average molecular weight retention rate measured by CPC.

Regarding light resistance, the same film was irradiated with 3BOnm carbon arc ultraviolet rays for 25 hours using a fade meter, and the tensile strength retention rate after that was evaluated.

Regarding oxidative deterioration resistance, TGA (in air, 10°C
The temperature was evaluated based on the thermal decomposition initiation temperature (temperature increase per minute).

Elastic recovery was evaluated by stretching a 100μ polyurethane film by 300% in about 90 seconds at room temperature, holding it for about 90 seconds, then contracting it suddenly, measuring the length, and determining its permanent elongation rate. .

Regarding intrinsic viscosity, polyurethane was added to 100mf of dimethylacetamide solution at 0.02g, 0.05g, 0.
．． A polyurethane solution containing 1 g dissolved therein was prepared, the reduced viscosity was measured at 30°C, and the polyurethane concentration was extrapolated to zero.

Examples 9 to 11 Aliphatic copolycarbonate diols A-C (PC -A-PC-C) was obtained. each o
The H value was as shown in Table 2.

Table 2 Note: 1,4-BD stands for 1,4-butanediol, 1.5
-PD is 1,5-bentanediol.

Comparative Example 1 Polycarbonate diol was obtained in the same manner as in Example 1 except that 944 g (8.0 mol) of 1,6-hexane diol was used. The OH value was 55.0. (abbreviation PC-
D) Comparative Example 2 Same as Example 1 and 1,6-hexanediol 47
2 parts (4.0 mol), 1,4-butanediol 360
(4.0 mol) was used to obtain copolycarbonate diol-L (abbreviated as PC-E). The OH value was 58.1.

Examples 12 to 15 and Comparative Examples 3 to 6 PC-A - PC-D shown in Examples, Asahi Kasei ■
Polytetramethylene glycol (01 (value 5) synthesized in
9.6, abbreviated as PTMG), polytetramethylene adipe) (manufactured by Dici, 08 value 58.3, abbreviated as PTA) (made by pressure top and bottom dehydration treatment). 4 times the weight of toluene/M
It was dissolved in IBK (1/1wt/wt) and heated to 100°C (the weight of the preparation is shown in Table 3).

Next, a predetermined amount of hexamethylene diisocyanate (HD
r) or diphenylmethane-4,4'-diisocyanate (abbreviated as MDI) in toluene/old B in an amount equal to the weight of the diisocyanate (1/1wt/1vt) to prepare the above polyol. It was added to the solution and mixed (the amount to be added is shown in Table 3).

Next, 10% by weight toluene/M of dibutyltin laurate
An IBK (1/1wt/1vt) solution was added to the solution at a concentration of 100 ppa+ relative to 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 the chain extension side of either 1,4-butanediol or ethylene glycol was added to toluene/MIBK (1
/1wt/wt) (The location of the solvent is such that the solids in the solution are 25%
(adjusted to % by weight) and added to 100°
Stir strongly for 1 hour at C. The amount to be added is shown in Table 3),
A 5% by weight polyurethane solution was obtained.

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

(Margin below) Example 16 and Comparative Examples 7 to 1O PC-^, PC-D, PC-E, PTMC,
2 moles each of polyhexamethylene neopentylene adipate (manufactured by Bayer AG, 08 value 56.0, abbreviated as PHNA) and 4 moles of diphenylmethane-4,4'-diisocyanate were added at 80°C under a nitrogen stream without solvent. The reaction was carried out under stirring for 4 hours to produce an isocyanate-terminated prepolymer, which was then cooled to room temperature and sufficiently dehydrated dimethylacetamide was added thereto to dissolve it. A dimethylacetamide solution in which 2 moles of ethylenediamine had been dissolved was added all at once to this solution, and the mixture was stirred at room temperature for 30 minutes to obtain five types of 30% polyurethane solutions. A portion of the polyurethane solution was cast to obtain a 100 μm film, and data on hydrolysis resistance, light resistance, oxidative deterioration resistance, and elastic recovery were obtained. The results are shown in Table 4.

Furthermore, an attempt was made to spin most of the polyurethane solution using a small spinning device to obtain bottle urethane fibers. The results are shown in Table 4.

〔Effect 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 has extremely excellent properties, with high chemical stability and excellent rubber properties. This is an unprecedented high-performance polyurethane that combines excellent properties.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. As a repeating unit, A: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and B: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the ratio of A and B is 9:1 ~ 1:9 copolycarbonate with a number average molecular weight of 300 to 50,000. 2. A/B of copolycarbonate is 75/25 to 25
/75. 3. The copolycarbonate according to claim 1 or 2, wherein the terminal end of the copolycarbonate is selected from a hydroxyl group, an acryloyl group, a methacryloyl group, an allyl group, an alkyl carbonate group, and an aryl carbonate group. 4. Repeating unit A: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ and B: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Number average molecular weight in which the ratio of A and B is 9:1 to 1:9 A polyurethane containing 300 to 50,000 copolycarbonates as constituent units.