KR910007586B1 - Polyurethane urea amide elastomer of low hardness - Google Patents

Abstract

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Description

[Name of invention]

Low Hardness Polyurethane Urea Amide Elastoma

Detailed description of the invention

[Industrial use]

The present invention is a low-hardness polyurethane urea amide elastomer as an example of low-hardness, such as automotive interior parts such as armrests, and also requires flexibility, shoes insoles, knee guards, vibration absorbers of audio equipment, machinery It has a use, such as a shock absorber.

[Prior art]

Conventional low-hardness polyurethane elastomers are used as a buffer material (shock absorbing material) produced by a known method (complete short method, prepolymer method).

The required properties of the low hardness polyurethane are shock absorbing (shock absorbing) vibration resistance characteristics.

Substitution characteristics for evaluation of buffering properties include hysteresis loss, resilience, and vibration fatigue resistance characteristics such as tear strength, bending, and extension test. In other words, as a buffer, a high hysteresis loss and a high tear strength are required.

In the case of the conventional low hardness urethane elastomer, the hysteresis loss increases as the NCO index is lowered. On the contrary, it is difficult to obtain a satisfactory material because the tear strength is very low and the heat resistance is low. Ratio in a firewood (Japanese Patent Application No. 61-303) mainly containing a poly (urethane) urea (amide) group polymer containing a polymer obtained by the reaction of a polyether polyol derivative and a polyisocyanate for the purpose of improving heat resistance. Foamed elastomers are not produced with hardness lower than 60.

In order to improve the heat resistance, the polymer obtained by the reaction of the polyester polyol derivative and the polyisocyanate and the non-foamed polyurethane urea amide elastomer obtained by the production method thereof (Japanese Patent Laid-Open No. 61-126124) have a hardness of 55 or less. It is not manufactured.

[Problem Solving Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low hardness polyurethane urea amide elastomer having excellent buffering properties, vibration resistance and heat resistance.

[Means to solve the problem]

This invention uses together at least 1 sort (s) of polyol derivatives of following (I)-(III), and polyoxypropylene glycol together as a polyol component in the polymer obtained by reaction of a polyisocyanate component and a polyol component. It relates to a low hardness polyurethane urea elmastoma excellent in thermal stability.

x＜(n-1)의 수, y : 평균치에 따른 0.05

y＜1의 수]로 나타내지는 폴리에테르 폴리올 유도체.[A: n-valent polyoxyalkylene polyol residue obtained by subtracting a hydroxyl group from n-valent polyoxyalkylene polyol of molecular weight 400-10,000, integer of n: 2-8. x: 0 according to the mean

x <(n-1) number, y: 0.05 according to average value

The polyether polyol derivative represented by y <number of 1.

기를 가진 m가의 폴리에스테르 폴리올에서 말단 시원자를 제함으로서 얻어지는 m가의 폴리에스테르 폴리올, m : 2

m

4의 정수, z : 평균치에 따른 0

z

(m-1)의 수, 주쇄중의

기의 -NH-기는 아미노 안식향산의 카보닐잔기 및/또는 폴리에스테르 폴리올 다염기산의 카보닐잔기와 인접하여 아미드기를 형성하고, -CO-기는 에스테르기 또는 아미드기를 형성한다.]로 나타내지는 폴리에스테르 폴리올 유도체.[B: in the main chain of molecular weight 400-10,000

M-valent polyester polyol obtained by subtracting a terminal atom from a m-valent polyester polyol having a group, m: 2

m

Integer of 4, z: 0 according to the mean

z

number of (m-1) in the main chain

The -NH- group of the group forms an amide group adjacent to the carbonyl residue of the amino benzoic acid and / or the carbonyl residue of the polyester polyol polybasic acid, and the -CO- group forms an ester group or an amide group. derivative.

As the elastomer obtained by the present invention, preferred is (JIS-A) of 55 or less. For example, when used in the armrest of an automobile part, the feel of the armrest is very good, and the hardness (JIS-A) 20 The best grip is around -30. In addition, when used in the insole of the shoe, the feet do not feel the hardness of the elastomer and the sole of the sole during the exercise feels uncomfortable. The same is true of the knees of the legs.

The polyether polyol derivative of the general formula (I) of the present invention is, for example, by a method of de-alcoholization by transesterifying a polyoxy alkylene polyol and an amino benzoic acid alkyl ester described in JP-A-59-53533 Obtained.

In the above, it is most suitable to use 0.125-1.2 mol of amino benzoic acid alkyl ester with respect to 1 mol of n-valent polyoxy alkylene polyols. The polyether polyol derivative (I) obtained by this method may be an esterified body in which the terminal hydroxyl groups are all converted to an amino group, or a partial esterified body in which some unreacted hydroxyl groups remain, or the degree of esterification rate, that is, the degree of amine conversion rate is wide. Possible over the range and the preferred amine conversion is about 50-100%.

The general formula (II) polyether polyol derivative of the present invention is obtained by reacting, for example, the n-valent polyoxyalylene polyol and amino benzoate in the presence of an aliphatic alcohol described in Japanese Patent Application Laid-Open No. 60-208320.

In the above, it is most preferable to react 0.125n-2n moles of amino benzoic acid, preferably 0.5n-2n moles with 1 mole of n-valent polyoxyalkylene polyol in the presence of 0.125n-30n equivalents of aliphatic alcohol.

The polyether polyol derivative (II) obtained by this method has an esterified body in which the terminal hydroxyl groups are all converted to an amino group, or a partial esterified body in which some unreacted hydroxyl groups remain, and also contains an aromatic amide group adjacent to the terminal amino phenyl group. .

The degree of esterification, ie the amine conversion rate and the amidation rate, is possible over a wide range and the preferred amine conversion rate is about 50-100%, and the amide group adjacent to the amino phenyl group is preferably 10-50% relative to the terminal amino group.

As the most suitable polyoxyalkylene polyol to be used in the present invention, one kind of alkylene oxide such as ethylene oxide, propofylene oxide, tetrahydrofuran or the like in the presence of a suitable initiator such as water, low molecular weight polyol, low molecular weight amine or The polyether polyol of the 2-8 valent molecular weight which carried out addition polymerization more than that in arbitrary order can be mentioned, These can be obtained by a well-known method.

Suitable low molecular weight polyols as the above initiators include, for example, ethylene glycol, furopropylene glycol, 1.4 butanediol, 1.6 hexanediol, glycerin, trimerol furophane, penda erythritol, sorbitol, sucrose, hydroquinone, 2.2-bis (4-hydro) Roxy phenol) furopan etc. are mentioned, or low molecular weight amine includes methylamine, butylamine, ethylene diamine, aniline-triene diamine, etc., Alkanol amine, such as ethanol amine, diethanol amine, and triethanol amine Can also be used.

The amino benzoic acid used in the present invention may be any of ortho, meta or paraamino benzoic acid. Examples of amino benzoic acid alkyl esters include methyl benzoic acid, ethyl isofurophyll, n-furophyll, isobutyl, t-butyl, and amine esters. Of these, the foregoing methyl and ethyl esters are most suitable.

The aliphatic alcohol used in the present invention can be exemplified by various kinds, and preferred examples thereof include methanol, ethanol, propanol, butanol, nusanol, octanol, cyclobutanol, cycloheptanol, and cyclobutan. C1-C8 diols, such as cyclic monoalcohol, an cyclic monoalcohol, ethylene glycol, furpandiol, butanediol, hexanediol, and a heptandiol, etc. are mentioned. Or cellosolves, such as 2-butoxyethanol and 2-ethoxyethanol, are also suitable.

The polyester polyol derivatives of general formula (III) used in the present invention are those which contain aromatic amide groups in the main chain by partially or totally aromatic amination of the ends of the polyester polyols described in Japanese Patent Application Laid-Open No. 61-126124. The production is completed by the one-stage reaction, and the yield is high and does not require purification.

The polyester polyol derivative used in the present invention is obtained by reacting a polyester polyol having a molecular weight of 400 to 10,000 with an amino benzoate and an amino benzoic acid alkyl ester.

The polyester polyol used for this invention may either be a condensed-type polyester polyol and a lactone-type polyester polyol obtained by a well-known method. Condensed polyester polyols include saturated or unsaturated dibasic acids such as adipic acid, sebacic acid, terephthalic acid, isobutyric acid, maleic acid, and fumaric acid, acid anhydrides such as maleic anhydride and phthalic anhydride (dimethyl terbutalic acid). Polyester polyols obtained by condensation reactions of dialkyl esters with glycols such as methylene glycol, furopropylene glycol, butylene glycol, diethylene glycol, difuropropylene glycol, neopentyl glycol, 1,6 hexylene glycol, and the like. Examples include adipate-based polyols made of one type of acid and one type of glycol, such as polyethylene adipate polyol, polybutylene adipate polyol, polyhexylene adipate polyol, polyethylene butylene adipate polyol, polyethylene diethylene adipate polyol, polyhex One kind of acid such as styrene neopentylene adipate polyol and many kinds of glee Polyethylene adipate terephthalate Gupta rate polyols, there may be mentioned aromatic polyols such as polyethylene adipate rate iso butanoyl rate polyol.

The lactone polyester polyol is obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-butyrolactone, but becomes a polyol having various compositions depending on the type of initiator.

As the initiator, polyether polyols such as glycols such as ethylene glycol and butylene glycol, polyoxyfuropropylene glycol (PPG) and polyoxy tetramethylene glycol (PTMG), and condensed polyester polyols such as adipate are selected. Any of these may be used in the present invention.

Moreover, the bifunctional or more than polyfunctional polyol of condensation system polyester polyol and lactone system polyester polyol is also suitable for this invention. Examples include condensed polyester polyols, polyester polyols using glycerin or trimethylol furopane in one glycol component or polybasic acids such as trideracic acid in one part of dibasic acid, and lactone polyester polyols. Polyester polyol obtained by using glycerin and trimethyl as propane, pentaerythritol, or the like as the ring-opening polymerization initiator may be used in the present invention.

When the polyester polyol derivative obtained by it among the said polyester polyol is used for an elastomer synthesis raw material, the 2-3 polyvalent polyester polyol of the molecular weight 1,000-4,000 is the most suitable.

In addition, when it is used for synthetic raw materials of plastics, the most suitable is a 3-4 valent polyester polyol having a molecular weight of 400-1,500, for example, a lactone polyester polyol obtained by using pentaerythritol as an initiator.

The amino benzoic acid alkyl esters used in the present invention may be any of ortho, meta or paraamino benzoic acid alkyl esters, but in the case of using the polyester polyol derivative of the present invention in the synthetic raw materials of elastomer and plastic, Ester is particularly suitable.

Examples of the alkyl group of the amino benzoic acid alkyl ester can be exemplified by various alkyl groups, and examples of the alkyl group of the amino benzoic acid ester include those having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, nucleus, cyclobutyl, cyclopentyl, and heptyl; Alkyl may be mentioned. Or 2-butoxyethyl, 2-ethoxyethyl, etc. are also suitable. Or bis (amino benzoic acid) alkyl esters may also be used.

Bis (amino benzoic acid) esters, such as glycol of 2-8 carbon atoms, such as ethylene glycol, furopropylene glycol, butylene glycol, hexylene glycol, heptylene glycol, are suitable.

In the present invention, it is suitable that m is reacted with 0.25 m-10 mmol, preferably 0.5 m-2 mmol, with respect to 1 mol of polyester polyol.

The polyester polyol derivative of the present invention is obtained by heating to 150-250 ° C and dealcoholization, usually by adding an inert gas such as nitrogen gas in the presence of a non-catalyst or a known esterification catalyst. In the case of using a catalyst, a weakly acidic or weakly basic catalyst which has little influence as an ester bond in a polyester polyol and is less likely to cause side reactions such as dehydration of hydroxyl groups, for example, metal oxide tetraisopurophyll titanium such as antimony trioxide Organic titanium compounds, such as nate and tetrabutyl titaniumate, and weak acid alkaline earth metal salts, such as calcium acetate, etc. are contained, Among these, an organic titanium compound is suitable.

The amount of catalyst is usually 1,000 PPM or less. In addition, you may use coloring agents, such as an inert catalyst and triphenyl phosphate, in reaction. The reaction is continued until the end of the outflow of aliphatic alcohol and the system is depressurized thereon to completely remove excess amino benzoic acid alkylester residues that may be present with the alcohol. Tablets are not particularly needed. Rather, it should be noted that the reaction between the polyester polyol and the amino benzoic acid alkyl ester simultaneously occurs in the transesterification reaction of the polyester polyol with the amine group of the terminal hydroxyl group or the amino benzoic acid alkyl ester or in the amide formation reaction. There is work going on.

These two reactions can be controlled by adjusting the reaction temperature, the molar ratio of the polyester polyol and the amino benzoic acid alkyl ester or the time required for the de-alcohol. Therefore, the polyester polyol derivative obtained by the reaction of the polyester polyol and the amino benzoic acid alkyl ester of the present invention is a compound having a molecular weight that differs from the molecular weight of the polyester polyol introduced and the calculated molecular weight obtained from the amino benzoic acid alkylester dosage. In order to obtain a polyester polyol derivative having a desired molecular weight, attention should also be paid to the input amount of the raw material.

The content of amide groups is an important factor for achieving the production of polymers having better heat resistance and stronger mechanical strength for the purposes of the present invention. The aromatic amide group formation reaction is not yet fully understood, but is inferred by the following.

Formula (1) is reaction of terminal amination, and formula (2) is reaction in which the aromatic amide group adjacent terminal amino phenyl group is formed.

Formula (3) is a reaction in which an aromatic amide group is inserted in a polyester main chain.

Formula (4) is reaction which the aromatic amide group changed in the polyester main chain which has aromatic amide group is inserted.

Aromatic amide groups in the polyester polyol derivatives can be identified quantitatively by analysis by and nitrogen element analysis.

In the case of using an aliphatic polyester polyol as a starting material, the amide group in the polyester polyol derivative of the present invention can be estimated based on the results of ¹³ C-NMR analysis.

Since the difference between the number of two ester groups, that is, the difference between the terminal amino benzoic acid ester group and the number of ester groups in the main chain is large, the probability of the reaction occurring is naturally larger in the main chain.

For this reason, it is considered that the amide formation reaction in the polyester main chain is predominant.

The polyester polyol derivatives obtained by the method of the present invention contain an aromatic amide group in the main chain since there is an esterified body in which the terminal hydroxyl groups are all converted to an amino group, or a partial esterified body in which some unreacted hydroxyl groups remain. The degree of amination rate (i.e., esterification of terminal hydroxyl groups) and amidation rates can range over a wide range depending on the application, and on average, at least one hydroxyl group of the polyester polyol needs to be esterified and a preferred amination rate is about 50. -100% is correct and the amide group is varied over a range of about 5-2000 mol% relative to the terminal amine group, but about 5-100 mol% is suitable. In this range, the amide group has a suitable viscosity of the polyester polyol derivative and is excellent in moldability.

According to the present invention, when ethylene adipate is used as the raw polyester, an example of a derivative is given by the following formula.

However, in the formula, each segment does not indicate the order of bonding but represents a ratio, and -NHC ₆ H ₄ CO-groups in the main chain are randomly bonded instead of blocks, and may or may not be bonded to the terminal amino benzoyl group.

R ₁ : CH ₂ CH ₂

R ₂ : CH ₂ CH ₂ CH ₂ CH ₂

fz

1의 수z: The value represents the average singer 0

fz

Number of 1

P. r

k의 수P. r: Average of repeated number of structural units, 0

P. r

number of k

q

10의 수. 반복되는 수는 아니다.q: As an average value showing the number of structural units contained in one molecule, 0.05

q

10 numbers. It is not a repeating number.

k: Definition number p + r = k determined by molecular weight

Moreover, an example of the polyester polyol derivative of general formula (I) at the time of using the riol obtained as ring-opening polymerization of -caprolactone as a raw material is shown by a following formula.

R ₃ : CH ₂ CH ₂ CH ₂ CH ₂ CH ₂

R ₄ : alkyl group such as CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ CH ₂

z

1의 수z: The value represents the average singer 0

z

Number of 1

s.u.v

k의 수su v: the average value of the repeating number of structural units, 0

suv

number of k

t

10의 수. 반복되는 수는 아니다.t: Average value which represents the number of structural units contained in 1 molecule, 0.05

t

10 numbers. It is not a repeating number.

k: The number of the definition number s + u + v = k determined by molecular weight is not limited to the structure of the polyester polyol derivative of the present invention as an example in the case of using a bifunctional polyester polyol.

Any known polyisocyanate may be used according to the polyurethane chemistry such as the polyisocyanate used according to the present invention. For example, hexamethylene diisocyanate, isophorone diisocyanate, 4.4 'dicyclohexyl methane diisocyanate (NDI) 2.4 tolylene di Isocyanates (2.4 TDI) 2.6 Toylene Diisocyanate (2.6 TDI) 4.4 'Diphenylmethane Diisocyanate (MDI) Carbodiimide Modified MDI, Polymethylene Polyphenyl Polyisocyanate, Ortho-Tolidine Diisocyanate (TOD) Naphthalene Diisocyanate (NDI) Xylene diisocyanate (XDI) etc. can be mentioned, One type or two or more types can be used.

Among them, suitable polyisocyanates include 2.4-TDI, 2.6-TDI, MDI, carbodiamide-modified MDI, PAPI, TODI, and NDI.

According to the present invention, the desired poly (urethane) urea (amide) polymer can be obtained by using each of the above components and polyoxyfuropropylene glycol (PPG), but then a chain extender and / or a long chain polyol may be You may use it.

Examples of the chain extender include diamines having a 2-4 functional polyol having a molecular weight of 400 or less and a primary or secondary terminal amino group having a molecular weight of 400 or less.

Suitable chain extenders include, for example, (a) ethylene glycol, diethylene glycol, furophilene glycol, difurolene glycol butanediol, hexanediol, glycerin, trimethinol furophane, heptaerythrido, solidol, 1.4 cyclohexanediol Polyols, such as 1.4 cyclohexane dimethanol and xylene glycol, (b) hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1.4cyclohexanediamine, phenylenediamine, xylenediamine, 2.4 tolylenediamine, 4.4 Diamines such as aminodiphenyl methane, 3.3'-dichloro, 4.4'-diaminodiphenylmethane, 1.4-dichloro-3.5-diamino benzene, 1.3-furopandiol diparaamino benzoate, (c) ethanol amine, Alkanol amines such as diethanol amine and triethanol amine, (d) hydroxynon, pyrocalol, 4.4'-isopuropyridene diphenol, aniline and the above polyols, diamines, alkanol amines, and the like And the like Id and / or ethylene oxide, the polyol having a molecular weight of 400 or less obtained by adding in any order, and Of these diamines may develop an effect of the present invention. As the long-chain polyol, a polyol having two or more active hydrogens having an average molecular weight of 500-5000 is preferable, but various polyester polyols, polyether polyols, polycarbonate polyols, polymer polyols and the like may be used.

Specific examples of the polyester polyol include, for example, adipate-based polyols such as polyethylene adipate polyols, polybutylene adipate polyols, and polyethylene propylene adipate polyols, terephthalic acid-based polyols (e.g., Japanese Oriental Spinning Company, trade name Byron RUX, Byron). RV-200L, polycaprolactone polyols (e.g., DICEL Chemical name Flaccel 210, Flaccel 220), polyester polyols with neopentyl moieties or their copolymerized polyester polyols and 2 using trimethylol propane as glycol component Polyester polyol etc. which are more than a functional can be illustrated.

Specific examples of the polyether polyols include polyoxy ethylene glycol, polyoxy ethylene polyoxy propylene glycol, polytetramethylene glycol (except P.P.G), and the like.

As the polycarbonate polyol, polybutylene carbonate polyol polyhexane ethylene carbonate carbonate polyol is preferable. Plymer polyol is a graft polymerized monomer having a vinyl group on a polyether polyol, and specific examples thereof include, for example, 31/28 /, 32/30, 34/45, 36/28, 40 / 45 etc. are mentioned.

In the present invention, at least one of the above-described polyol derivatives (I)-(III) and PPG are used together as a polyol component. The elastomer obtained in the present invention having a good hardness (JIS-A) of 55 or less preferably has a PPG content of 10% or more in the elastomer of the present invention, particularly 30-70%.

In addition, NCO index should be 1.0 or less.

If the NCO index exceeds 1.0, the hardness exceeds 55, which is not good for insoles.

Furthermore, according to this invention, a plasticizer can be added as needed and it is most suitable to add to a polyol component normally. Although the following can be illustrated as a plasticizer, It is preferable to mix | blend about 5-10 parts with respect to 100 parts of R liquids (it is equal to below a weight ratio) generally.

Phthalic acid ester system:

Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate dibutyl-phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, dinonyl Phthalate, diisodecyl phthalate dietridecyl phthalate, dicyclohexyl phthalate and the like.

Aliphatic dibasic acid ester type:

Succinic dioxodecyl, adipic acid dioctyl, adipic acid diisodicazelic acid dioctyl, sebamic acid dibutyl sebamic acid dioctyl, tetrahydrophthalic acid dioctyl,

Glycol ester system:

Diethylene glycol dibenzoate and the like.

Fatty acid ester system:

Butyl oleic acid, methyl, acetyl, ricinolate, methyl chlorinated fatty acid, methoxy chlorinated fatty acid methyl and the like.

Phosphoric acid ester system:

Tricresyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate and the like.

Epoxy type:

Epoxidized soybean oil, epoxidized linseed oil, epoxy, butyl stearate, octyl epoxy stearate, pentyl epoxy stearate, dioctyl epoxy nucleus hydrophthalic acid, and the like.

Phthalic acid mixed ester series:

Butyl butyrate, benzyl, butyl lauryl butyrate, methyl ore butyrate, and the like.

Other :

Trimeryl trioctyl, ethyl phthalyl ethyl glycolate, butylphthalic-butyl glycolate, acetyl citrate tributyl, chlorinated paraffin, chlorinated n-paraffin, polypuropropylene adipate, polypuropropylene sebagate, triacezin, tributyl Lean, triensulfone amide, alkylbenzenes, diphenyl camppoles and the like.

In the present invention, the production of the polyurethane urea elastomer can be applied under good conditions to the one-shot method and the prepolymer method as well as the known method. For example, the preparation of the prepolymer method is performed by mixing the polyisocyanate with the polyol in advance at about 60-90 ° C. for 30 minutes to 4 hours, adding the remaining polyol and a chain extender as necessary, and mixing the same. Therefore, it is degassed and the uncured reaction solution is heated to about 60-150 ° C. to cure until it does not flow out of the mold.

The cured molded article is then demolded to terminate the postcure core reaction at about 60-150 ° C. for about 30 minutes-20 hours.

[Effects of the Invention]

In the present invention, at least one of the specific polyol derivatives (I)-(III) and PPG is used as the polyol component, and the low-hardness polyurethane urea amide elastomer in which the polymer obtained by the reaction with the polyisocyanate is introduced is hysteresis loss. In addition, it is possible to obtain an excellent buffer in which the tear strength is not remarkable as compared with the low hardness polyurethane elastomer which does not introduce these polymers. Even if the hysteresis loss is increased due to the high content of the elastomer of such a polymer, the tear strength is low and the deceleration rate is low, and the thermal stability is excellent because the polymer content is high.

EXAMPLE

Next, a reference example, an Example, a comparative example, and a test example are given and demonstrated.

Reference Example 1

Polyether Polyol Derivatives (I)

Polytetramethylene glycol (PTMG 1,000 1035, manufactured by Mitsubishi Chemical Corporation) 502 g 160 ml of paraamino benzoic acid and 0.13 g of tetrabutyl titanate were added to a three-necked flask with dry nitrogen gas, and when the temperature reached 180 ° C, ethyl alcohol began to flow out. do.

When the temperature is gradually raised to 200 ° C, the distillation of ethyl alcohol reaches 82% of the theoretical amount. Then, the temperature is raised to 215 ° C, held for 2 hours, and the pressure is reduced to remove unreacted paraamino benzoic acid ethylol. This yields a polyether polyol derivative having an amine value of 1.42 meq / g, an amino group, a hydroxyl group and a total of 1.594 meq / g.

89.5% of the terminal hydroxyl groups of the polyol are converted to amino groups.

Reference Example 2

Polyether Polyol Derivatives (II)

Polyoxytetramethylene glycol (PTMG 1500 MW 1498 manufactured by Mitsubishi Chemical Corporation, Ltd.) 3000 g (4.01 eq) paraamino benzoic acid (Hangay Chemical reagent GR) 632 g (4.61 eq) 2-ethyl-1-nucleool (octanol) 0.6 g of 520 g (3.99 eq) terabutyl titanium acetate was heated while blowing dry nitrogen gas in a four-necked flask to obtain a temperature of 215 ° C., to which 2-ethyl-1-hexanol was refluxed. -Drop the water drop into the separating tube attached to the lower part of d.

Next, when heating is continued and maintained for 6 hours in the range of 215-230 degreeC, 73.5 g of water flows out by reaction.

Next, 2-ethyl-1-hexanol was removed at a temperature of 200-210 ° C. under a reduced pressure of 17-110 mmHg, and then heated to 220-240 ° C. to 2-ethyl-1-nucleic acid under a reduced pressure of 2.5-3 mmHg. When removed, a reddish brown liquid having a viscosity of 9,500 CPS is obtained. The quantity is 2103 is correct. When this liquid is analyzed by gel permeation chromatography, free paraamino benzoic acid and paraamino benzoic acid octyl ester are hardly detected. Alternatively, the liquid was confirmed to generate a polyether derivative having a terminal amino group using the following analysis method.

In other words, the titer of perchloric acid in glacial acetic acid (Analysis Chemistry Handbook, Rev. 3rd edition 261 pages) shows an amine number of 1.802 meq / g.

In addition, according to the measuring method (JIS K 1557), the total amount of hydroxyl groups and amino groups is 1.169 meq / g.

Analysis of this product by gel filtration chromatograph detects free paraamino benzoic acid and paraamino benzoic acid octyl, provided that the molecular weight distribution of the peak is approximately equal to PTMG 1500 of the starting material.

Thus, the terminal hydroxyl group of PTMG 1500 is converted to 92.6% amino group. ¹³ C-NMR analysis of the product confirmed the presence of the amide group.

The containing amide group is 11.5% present relative to the terminal amino group. Thus, the elemental analysis of nitrogen is 1.73%. On the other hand, the nitrogen content is 1.15% based on the amine group calculated | required by calculation in the amine number.

Reducing the amount of nitrogen contained in the amine number (%) from the elemental nitrogen analysis value yields the amount of the contained amide as nitrogen based on the amide group and exists 12.4% of the terminal amide group.

^The amount of amide contained in the ¹³ C-NMR analysis and the amount of contained amide obtained in the elemental analysis were different in the analytical method, so that no consistent value was obtained, but none showed more than 10% of the amide group.

Reference Example 3

Polyester polyol derivative (III)

Lactone polyester polyol (Placel-210 Daicel Co., Ltd. MW 990. OH.V. 2.02 meq / g) 2442 g (4.935 eq) was added to a stirring rod, a cooling tube, a thermometer, and a nitrogen gas introduction tube. Into an old flask, nitrogen gas is blown for 1 hour at 100 ° C to dehydrate.

Next, ethyl paraamino benzoate (570.5 g (3.46 moles) of the first-class drug present by Hankei Chemical Co., Ltd.) is added, and the temperature is raised to 88 ° C.

Next, 1.025 g (340 PPM) of tetrabutyl titanate was added thereto, followed by stirring and heating. At 110 ° C, the reaction system became a homogeneous solution and wetted with ethanol in which the wall surface of the four-necked flask was formed.

Next, the temperature was continued and the reaction was continued for 3 hours and 30 minutes in the temperature range of 225-230 ° C. to maintain ethanol.

The reaction system is then cooled to 138 ° C and depressurized to 7 mmHg under a stream of nitrogen gas. The system is heated up to 200 ° C. and unreacted ethyl paraimino benzoate is removed for 3 hours to give a reddish brown liquid having a viscosity of 11,000 CPS at 30 ° C. The yield is 2854g. When this liquid is analyzed by gel permeation chromatography, free ethyl ethyl benzoate is not detected.

The liquid was then analyzed using the following analytical method to confirm the production of a polyester polyol derivative having a terminal amino group.

In other words, the amine titer becomes 0.998 meq / g by titration with perchloric acid in glacial acetic acid (Analysis Chemistry Handbook Rev. 3rd Edition 261 pages).

In addition, according to the measuring method (JIS K 1557), the hydroxyl value which measures the total (active hydrogen value) of a hydroxyl group and an amino group is 1.277 meq / g. These measurements do not coincide with 1.728 meq / g of amine value 1.213 meq / g active hydrogen group calculated from the dosage of polyester polyol and ethyl paraamino benzoate.

The molecular weight of the polyester polyol derivative having a terminal amino group at 1.277 meq / g of the measured active hydrogen group was 1566. When the product was analyzed by gel permeation chromatography, it was confirmed that the molecular weight distribution shifted to the polymer side compared to the raw polyester polyol. .

Moreover, ¹³ C-NMR analysis of this product confirmed the presence of an amide group, and the amide group exists in 20 mol% with respect to a terminal amino group.

In addition, elemental analysis shows that nitrogen is 1.68% and is consistent with the amount of amide (total nitrogen-amine) calculated therefrom.

From these results, the polyester polyol derivative of the product is a compound in which 78.2% of the terminal hydroxyl groups are converted to amino groups and at the same time contain 20 mol% of aromatic amide groups relative to the terminal amino groups in the molecular chain.

The average structure of the product is estimated in the following state.

MW 1566, a + b + c = 11.2

Example 1

Polyether polyol derivative (I) 12.6 parts polyoxypropylene glycol [Exenol 540 by Asahi Choza Co., Ltd., molecular weight 2,000, hydroxyl value 56.1] 49.4 parts Polyoxy puropylene glycol (Exenol 330 by Asahi Choza Co., Ltd., molecular weight 300, hydroxyl value 560 15.8 parts polyoxyfuropropylene glycol [Exenol 902 made by Asahi Choza Co., Ltd., molecular weight 1,500, hydroxyl value 112] 15.8 parts dioxyphthalate, 6.3 parts Triethylene diamine R liquid is adjusted by the ratio of 0.05 parts. (The adjusted hydroxyl value of R is 145.3)

Mixing and stirring the carboxy imide-modified MDI (MTL made by Japan Polyurethane Industry Co., Ltd., NCO content 28.8%) and the adjusted R liquid at the predetermined mixing ratio shown in the first table by changing the NCO index into the shape shown in the first table. After degassing, the mold was cast in a mold preheated to 90 ° C., cured in an oven at 90 ° C., demolded after 1 hour, and then post-cured for 2 hours to obtain a polyurethane urea amide elastomer.

TABLE 1

Example 2

Polyether polyol derivative (I) 25.5 parts, PPG (Exenol 540) 36.3 parts, PPG (Exenol 330) 15.9 parts, PPG (Exenol 902) 15.9 parts, dioctylphthalate 6.4 parts and triethylene diamine 0.06 parts Adjust the amount of R. (The adjusted liquid hydroxy group is 150.3.) The NCO index is changed to the shape of the second table, and the carboxyimide-modified MDI (MTL, NCO content 28.8%) and the adjusted R solution, both heated to 40 ° C., are mixed and stirred at the predetermined mixing ratio in the second table. After degassing, it is cast in a mold preheated to 90 ° C., cured in an oven at 90 ° C., followed by demolding after 1 hour, and then post cured for 2 hours to obtain polyurethane urea amide elastomer.

TABLE 2

Example 3

38.5 parts of polyether polyol derivative (I), 23.1 parts of PPG (Exenol 540), 16.1 parts of PPG (Exenol 330), 16.0 parts of PPG (Exenol 902) 6.4 parts of dioctylphthalate and 0.05 parts of triethylene diamine R Adjust the liquid. (The adjusted R-Ex hydroxyl value is 155.4.) The NCO index is changed to the shape of Table 3, and the carbodiimide-modified MDI (MTL, NCO content 28.8%) and the adjusted R solution, both heated to 40 ° C, are mixed at the predetermined mixing ratio in Table 3. After stirring and degassing, it is cast in a mold preheated to 90 ° C., cured in an oven at 90 ° C., demolded after 1 hour, and then post cured for 2 hours to obtain polyuretan urea amide elastomer.

TABLE 3

Example 4

R at a ratio of 25.2 parts of polyether polyol derivative (II), 36.9 parts of PPG (Exenol 540), 15.8 parts of PPG (Exenol 330), 15.7 parts of PPG Exenol 902), 6.3 parts of dioctylphthalate and 0.05 parts of triethylene diamine Adjust the liquid. (The adjusted R liquid hydroxyl value is 143.6.) The NCO index is changed to the shape of the fourth table, and the carbodiimide-modified MDI (MTL, NCO content 28.8%) heated at 40 ° C is mixed and stirred at the predetermined mixing ratio of the fourth table. After degassing, the mold is preheated to 90 ° C, cured in an oven at 90 ° C, demolded after 1 hour, and then post cured for 2 hours to obtain polyurethane urea amide elastomer.

TABLE 4

Example 5

At a ratio of 25.3 parts of polyester polyol derivative (III), 36.8 parts of PPG (Exenol 54), 15.8 parts of PPG (Exenol 330), 15.8 parts of PPG (Exenol 902), 6.3 parts of dioctylphthalate and 0.05 parts of triethylene diamine Adjust the amount of R. (The adjusted R liquid hydroxyl value is 145.3.) The NCO index is changed to the shape of the fifth table, and the carbodiimide-modified MDI (MTL, NCO content 28.8%) preheated to 40 ° C. is mixed with the adjusted R liquid at the predetermined mixing ratio of the fifth table. After stirring and degassing, it is cast in a mold preheated at 90 ° C., cured in an oven at 90 ° C., and demolded after 1 hour, and then post cured for 2 hours to obtain a polyurethane urea amide elastomer.

TABLE 5

Example 6

12.8 parts of polyether polyol derivative (I), 12.8 parts of polyester polyol derivative (III), PPG (Exenol 540) 3531, 0.57 parts of 1.4 butanediol, 16.1 parts of PPG (Exenol 330), 16.0 parts of PPG (Exenol 902) The R liquid is adjusted at a ratio of 6.4 parts of dioctylphthalate and 0.05 part of triethylene diamine. (The adjusted R liquid hydroxyl value is 155.4.) Carbodiimide modification preheated to 40 ° C. by changing the NCO index to the shape of Table 6. MDI (MTL, NCO content 28.8%) and the adjusted R solution are mixed and stirred at the predetermined mixing ratio in Table 6, then degassed and cast into a mold preheated to 90 ° C, cured in a 90 ° C oven, demolded after 1 hour, and then 2 hours Postcure yields polyurethane urea amide elastomers.

TABLE 6

Comparative Example 1

Polytetramethylene glycol Mitsubishi Chemical Co., Ltd. product, PTMG 1,000, molecular weight 1,000, hydroxyl value 112.2 25.7 parts, PPG (Exenol 540) 35.7 parts, PPG (Exenol 330) 16.1 parts, PPG (Exenol 902) 16.0 parts R liquid is adjusted by the ratio of 6.4 parts of dioctyl phthalates and 0.05 parts of triethylene diamines. (Adjusted R liquid hydroxyl value 157.1) The NCO index was changed to the shape of Table 7, and the carbodiimide-modified MDI (MTL, NCO content 28.8%) and the adjusted R solution were all mixed at the predetermined mixing ratio in Table 7 After stirring and degassing, casting is carried out in a mold preheated to 90 ° C., and then cured in an oven at 90 ° C. for 1 hour after demolding, and then post cured for 2 hours to obtain polyurethane urea amide elastomer.

TABLE 7

[Test Example 1]

After curing the molded products of Example 1-6 and Comparative Example 1 at room temperature for 1 week, the physical properties thereof were measured according to JIS K 6301. Type B was used for tensile strength measurement.

In addition, the hysteresis loss measurement was performed using a graphic drawn on a chart of a special speed of 200 mm / minute, in which the No. 2 dumbbell-shaped sample was returned at the same head speed at the moment of 100% modulus of tension at a head speed of 100 mm / minute at room temperature. In Table 8, measurement results such as hardness, hysteresis loss and tear strength of Examples and Comparative Examples are shown.

In the table, each unit of measurement items is hardness (JIS-A), hysteresis loss (%), rebound elasticity (%), tear strength (kg / cm), and thermal stability is 100 ° C for 12 hours. When it did, it was O for maintaining a circular shape and X for not maintaining a circular shape.

TABLE 8

In Table 8, Comparative Example 1 is also possible through the hardness (JIS-A) 55 or less, which is considered to be the same as 1-6.

However, in order to use Comparative Example 1 as a shock absorber, when the NCO index is gradually lowered to increase hysteresis loss to lower the repulsive elasticity, the tear strength is lowered, and therefore, it is impossible to use it as an actual product in Comparative Example 1.

Example 1-6 has a larger hysteresis loss and a low rebound elasticity than that of Comparative Example 1, and the tear strength can be used as an actual product. In thermal stability, the elastomer blocks of each NCO index of Comparative Example 1 had a circular shape in which the original shape collapsed.

In contrast, it can be seen that the elastomers in the examples are excellent in thermal stability as they are in the same shape.

Example 7

Polyether polyol derivative (I) 38.5 parts, polytetramethylene glycol Mitsubishi Chemical Co., Ltd., pyrimage 2,000, molecular weight 2,000 hydroxyl group 56.1 23.1 parts, PPG (Exenol 330) 16.1 parts, PPG (Exenol 902) 16.0 In addition, R liquid is adjusted by the ratio of 6.4 parts of dioctyl phthalates and 0.05 parts of triethylene diamines. (Adjusted R solution hydroxyl value is 155.4) Mixing and stirring the carbodiimide-modified MDI (MTL, NCO content 28.8%) and the adjusted R solution with the NCO index heated to 40 ° C according to the shape of Table 9 After degassing, it is cast in a mold preheated to 90 ° C., cured in an oven at 90 ° C., and post-curing after 1 hour for 2 hours to obtain polyurethane urea amide elastomer.

TABLE 9

Example 8

38.5 parts of polyether polyol derivative (I), polytetramethylene glycol (PTMG 2,000, molecular weight 2,000, hydroxyl value 56.1) 23.1 parts, PPG (Exenol 330) 17.0 parts, polycaprolactone polyol Daicel Chemical Co., Ltd. The R liquid is adjusted by dividing the lacsel 320, the molecular weight 2,000, the hydroxyl value to 84.2 15.0 parts, the dioctylphthalate 6.4 parts, and the triethylene diamine 0.05 part. (Adjusted hydroxyl value of R solution 155.4) Carboimide-modified MDI (MTL, NCO content 28.8%) heated NCO index to 40 ° C according to the change in form of Table 10 and adjusted R solution, The mixture was stirred and then degassed and cast into a mold preheated to 90 ° C., cured in an oven at 90 ° C., after 1 hour, followed by post curing for 2 hours to obtain polyurethane urea amide elastomer.

TABLE 10

Table 11 shows the change in hardness at each NCO index of each example when the derivative content in the elastomer was made constant in the NCO index of each example and the PPG content in the elastomer was changed.

As a result, it can be seen that when an elastomer having a hardness (JIS-A) of 55 or less is made, the PPG content in the elastomer is 10% or more based on the index = 1.00. If it is less than 10%, the hardness is not better than 55.

According to the NCO index 1.0 of Example 8, it is possible to set the hardness (JIS-A) 55 or less even if the PPG in the elastomer decreases.

TABLE 11

Claims (5)

The polymer obtained by reaction of a polyisocyanate component and a polyol component WHEREIN: The thermal stability characterized by using together at least 1 sort (s) of polyol derivative of following (I)-(III) and polyoxypropylene glycol as a polyol component. Excellent low hardness polyurethane urea amide elastomer.

[A: n-valent polyoxyalkylene polyol residue obtained by subtracting a hydroxyl group from n polyoxyalkylene polyol of molecular weight 400-10,000, n: integer of 2-8, x: 0 according to the average value

X <(n-1) number, y: 0.05 according to average value

The polyether polyol derivative represented by y <number of 1].

[B: in the main chain of molecular weight 400-10,000

M-valent polyester polyol residual group obtained by subtracting terminal H atom from m-valent polyester polyol containing group, m: 2

m

Integer of 4, z: 0 according to the mean

z

number of (m-1) in the main chain

The -NH- group of the group forms an amide group adjacent to the carbonyl residual group of the amino benzoic acid and / or the polybasic acid carbonyl residual group of the polyester polyol, and the -CO group forms an ether group or an amide group. The low hardness polyurethane urea amide elastomer according to claim 1 using a chain extender and / or a long chain polyol having a molecular weight of 400 or less in the production of the polymer. The low hardness polyurethane urea amide elastomer according to claim 1 having a hardness (JIS-A) of 55 or less. The low hardness polyurethane urea amide elastomer according to claim 1, wherein the content of polyoxyfuropropylene glycol is 10% or more in the polyurethane urea amide elastomer. Low hardness polyurethane urea amide elastomer according to claim 1 having an NCO index of 1.0 or less.