JP2003528951A - Thermoplastic polyurethane elastomer (TPU) produced using polytrimethylene carbonate soft segment - Google Patents

Abstract

  (57) [Summary] Thermoplastic polyurethane elastomer (TPU) compositions are defined as a) poly (trimethylene carbonate) diol (PTMC diol) as a soft segment, b) diisocyanate, and c) diisocyanate reacting with glycol + total unreacted glycol. At least one glycol that reacts with the diisocyanate to form a hard segment of from 10 to 55% by weight of the composition.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to thermoplastic polyurethane elastomers (hereinafter referred to as TPU). More specifically, the present invention is a novel class of TPU made using poly (trimethylene carbonate) diol (PTMC diol) as the soft segment.
Regarding TPUs made with PTMC diols were extended with glycols, preferably low functionality glycols (including, for example, 1,3-propanediol and 1,4-butanediol).

BACKGROUND OF THE INVENTION TPUs are technically important because they provide high quality mechanical properties with the known advantage of being inexpensively thermoplastically processable. Mechanical properties can be varied significantly with various chemical components. TPU, its properties and uses are described, for example, in "Polyurethane Handbook", edited by Gunter Oertel, published by Hanser Publishers (1985), Munich, p.
． 405-417.

TPUs are composed of linear polyols (usually polyesters or polyethers), organic diisocyanates and short chain diols (chain extenders). The overall properties of TPU depend on the type of polyol, its molecular weight, the structure of the isocyanate, the structure of the chain extender and the ratio of soft to hard segments.

Polyurethanes can be thermoplastic or thermosetting depending on the degree of crosslinking present.
Thermoset and thermoplastic polyurethanes are either by the "one-shot" reaction of an isocyanate with a polyol, or by a "prepolymer" system in which a curing agent is added to a specifically reacted polyol-isocyanate complex to complete the polyurethane reaction. Can be formed. Thermoplastic urethanes do not have major crosslinks, whereas thermoset polyurethanes have varying degrees of crosslinks depending on the functionality of the reactants.

Thermoplastic polyurethanes are predominantly based on methylene diisocyanate (MDI) or toluene diisocyanate (TDI) and include both polyester and polyether grades of polyols. The polyol, chain extender and diisocyanate components can be varied within a relatively wide molar ratio range to adjust the properties.

To improve the processing behaviour, high stability and controllable melt flowability are very important, especially in the case of extruded products. It depends on the chemical and morphological structure of TPU. The structure required to improve processing behavior is usually obtained using a mixture of chain extenders (eg 1,4-butanediol / 1,6-hexanediol). As a result of this, the arrangement of the hard segments is largely deformed, which improves the melt flowability and at the same time the thermomechanical properties such as tensile strength and heat distortion resistance are often improved.

All known TPUs and blends containing TPUs have some in terms of one or more properties including mechanical properties, color stability to heat and light, transparency, heat deformability and phase separation. It has drawbacks. Often, attempts to improve one property, such as hardness, will deteriorate another property.

Thus, there are multiple problems in achieving hardness and related mechanical properties, stable color, transparency and high heat distortion temperature in TPU and blends containing TPU. There is a need in the art to find new compositions of TPU that provide a wide range of mechanical and thermal properties without compromising existing properties.

The present invention provides a new class of TPU compositions that offer new possibilities for mechanical and thermal properties including improved transparency and hardness, high elasticity, and improved softening temperature and coefficient of thermal expansion. It is useful in solving one or more of the problems of known thermoplastic materials by providing a TPU of

SUMMARY OF THE INVENTION The present invention provides a new class of TPUs with improved properties, which TPUs
Is a hard segment consisting of an isocyanate moiety that reacts with glycol and a glycol mixed with TPU and a diisocyanate for curing the system (
The main component is 1,3-propanediol) carbonate diol (PTNC diol). The hardness of the elastomer is slightly higher than the corresponding polyol-based TPU known in the art. The PTMC TPU exhibited good physico-mechanical properties including a slightly higher modulus than the control TPU. Abrasion resistance and compression set were very good, comparable to polyether TPU. It was found that the softening temperature and the coefficient of thermal expansion were improved compared to the control. In addition, with PTMC polyols, the transparency of the TPU could be improved and in some cases a completely transparent material could be obtained.

According to the above, the present invention relates to a) poly (trimethylene carbonate) diol (PTMC diol) as a soft segment, b) diisocyanate, and c).
At least one glycol (sometimes referred to as a chain extender) that reacts with the diisocyanate to form 10-55% by weight of the composition of a hard segment, defined as the sum of the diisocyanate moieties that react with the glycol and the unreacted glycol. Provided is a thermoplastic polyurethane elastomer (TPU) composition comprising.

[0012]     (Brief description of drawings)   Hereinafter, the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a graph showing the viscosity of polycarbonate polyol. FIG. 2 shows 1 of TPU containing 1,4-butanediol (1,4-BD) as a main component.
3 is a bar graph showing stress at 00% elongation. FIG. 3 is a bar graph showing the stress at a 300% elongation of TPU containing 1,4-BD as a main component. FIG. 4 shows a TPU containing 1,3-propanediol (1,3-PDO) as a main component.
3 is a bar graph showing the retention of tensile strength of the. FIG. 5 is a bar graph showing the weight change after immersion in water at 70 ° C. for 2 weeks. FIG. 6 is a bar graph showing the tensile strength at the initial stage and after immersion in water at 70 ° C. for 2 weeks. FIG. 7 is a bar graph showing the chemical resistance after immersion for 1 week.

DETAILED DESCRIPTION OF THE INVENTION A novel class of thermoplastic polyurethanes (TPUs) of the present invention are poly (trimethylene carbonate) diols as soft segments; hard segments containing glycols, preferably short chain glycols; and Prepared using diisocyanate. A suitable poly (trimethylene carbonate) diol was prepared by the method described below, and the samples used in the examples herein were characterized by a molecular weight of about 2000. The characteristics of the thermoplastic polyurethane containing PTMC diol as a main component were evaluated.

Aromatic and cycloaliphatic TPUs based on PTMC diol were prepared and evaluated. To produce the aromatic TPU is 4,4'-diphenylmethane diisocyanate (MDI), in order to produce aliphatic TPU methylene - using bis (4-cyclohexyl _{isocyanate) (H} 12 _MDI). The elastomer was manufactured using the one-shot method. In Examples 2, 3, 5 and 10, 1,3-PDO and 1,4-BD were used as chain extenders and in the Examples a hard segment concentration of 22 was used.
The range was changed to ˜35%. For comparison, commercially available poly (1,6-hexanediol carbonate) glycol (De, commercially available from Bayer Co.).
smophen C-200) and representative polyols used in the art were prepared and evaluated for TPU.

Physical and mechanical properties of TPU (hardness, stress-elongation properties, tear resistance, compression set,
Resilience and abrasion resistance) were investigated according to the ASTM standard method. Solvent resistance (paraffin oil, ethylene glycol and dilute acid / base) was examined by measuring the weight change upon immersion. The water resistance was evaluated by the retention of stress-elongation characteristics and the change in weight when immersed in water at 70 ° C.

The morphology of the elastomers includes thermal analysis and differential Fourier transform infrared (FTI) analysis including differential scanning calorimetry (DSC), thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA).
R). The transparency of the elastomer is 474 to 630 nanometers (nm
) Was also measured by measuring the light transmittance (%) in the visible range.

Due to the hardness of the PTMC diol, the elastomer exhibited a relatively high T _g (near 0 ° C.). Its hardness corresponds to the corresponding TPU, eg Desmophen C-
It was slightly higher than TPU containing 200, poly (tetramethylene oxide) (PTMG) 2000 or caprolactone polyol as a main component (see Tables 17 and 18).

The PTMC 2000 TPU showed good physical and mechanical properties. Its elastic modulus was higher than Desmophen C-200 TPU. PTMC 200
The wear resistance and compression set of 0 TPU were very good, comparable to polyether TPU.

PTMC 2000 TPU as indicated by its properties at high temperature, softening temperature and coefficient of thermal expansion
Was found to have improved thermal stability as compared to Desmophen C-200 TPU. By using PTMC 2000, the transparency of TPU can be improved and a completely transparent material can be obtained with H ₁₂ MDI.

The oil resistance of PTMC 2000 TPU was excellent and the resistance to other media such as dilute inorganic acids, bases and ethylene glycol was also excellent.

[0022]   Poly (trimethylene carbonate) polyol   Although higher functionality polyols may be used to make thermoset systems,
The TPU of the present invention is a PTMC diol prepared by the specific method in the Examples, and
Coles and diisocyanates are used. PTMC diol is the applicant
Manufactured as described in copending International Patent Application No. EP01 / 02323
I made it. The PTMC diols described here have substantially all end groups
It is a droxypropyl group, has no measurable allyl group, and has improved permeability.
Characterized by having lightness.

Poly (trimethylene carbonate) characterized by the desired properties mentioned above
For the preparation of trimethylene carbonate, trimethylene carbonate is reacted with a polyhydric alcohol in the presence of a catalyst, preferably in a nitrogen atmosphere. The polyhydric alcohol can be a diol, triol, a higher polyhydric alcohol such as propanediol and trimethylolpropane, or a mixture.

Poly (trimethylene carbonate) can also be prepared without a catalyst. However, the use of catalysts offers the advantage of shorter reaction times. Suitable catalysts are selected from salts of Group IA or IIA of the Periodic Table. Good results have been obtained with sodium acetate. Group IA or IIA catalyst is less than 1 ppm to 1000
It is expected that a small amount in the range above 0 ppm will be effective, but will normally be used in an amount in the range 5 to 1000 ppm, preferably about 10 to 100 ppm, and most preferably about 10 to 40 ppm.

Although it is preferred to produce the poly (trimethylene carbonate) without a solvent,
A solvent may be used.

Poly (trimethylene carbonate) is produced at temperatures in the range of 50-160 ° C. A preferred range is 100 to 150 ° C, more preferably 110 to 130 ° C. The pressure is not critical and practically almost any pressure can be used, but good results have been obtained at ambient pressure.

Poly (trimethylene carbonate) has properties that are determined by several factors. The most important of these factors are the type and amount of initial alcohol, the catalyst and its amount, and the manufacturing conditions. Manufacturers can vary the determinants to predictably obtain molecular weight, polydispersity and other properties required for a given application.

In the present invention, when producing a new class of TPUs that provide novel composition options, the molecular weight produced as described is less than about 10,000, preferably 1
Good results have been obtained with 000-3000 PTMC diols. The TPUs in the examples herein were made using PTMC diol with a molecular weight of 2000.

[0029]   Glycol (chain extender)   The glycol component is selected from aliphatic, cycloaliphatic, aralkyl and aromatic glycols.
Can be selected. As is well known to those skilled in the art, high functional alcohols are useful in many applications
Can be. However, the present invention uses low-functionality glycols for good binding.
The fruit was obtained. Examples of glycols used are ethylene glycol, propylene
Glycol, 1,3-propanediol, 2-methyl-1,3-propanedio
2,2-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl
Chill-1,3-propanediol, 2-ethyl-2-butyl-1,3-propane
Diol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-
Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 2,2,4-trimethyl-1,6-hexanediol,
Odiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexa
Dimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-teto
Lamethyl-1,3-cyclobutanol, p-xylene diol and mixtures thereof
Including but not limited to. Additional examples of suitable glycols include hydroquino.
Hydroxyalkyl derivative, i.e., bis 2-hydroxyethyl ether (
HQEE), and hydroxyalkyl derivatives of resorcinol and bisphenol A
A conductor is included. Preferred glycols are 1,3-propanediol and 1,4-butane.
It is selected from tandiol and mixtures thereof. Examples 2, 3, 5 and 10 are 1,
The use of 3-propanediol and 1,4-butanediol has been demonstrated.

The hard segment concentration is the sum of the portion of the isocyanate that reacts with the glycol and the unreacted glycol. The glycol hard segment is mixed with TPU in an amount corresponding to a concentration of 10-55%, preferably 20-40%.

[0031]   Isocyanate   Isocyanates used to cure polyurethane elastomers include
Usually, aliphatic, aromatic or cycloaliphatic polyisocyanates are included. TP of the present invention
Diisocyanate was used to produce U. Suitable diisocyanates are aliphatic
, Aromatic or cycloaliphatic diisocyanates. Examples of aliphatic diisocyanates
Is hexamethylene diisocyanate. Examples of cycloaliphatic diisocyanates include
, Isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1
-Methyl-2,4-cyclohexanediisocyanate, 1-methyl-2,6-si
Clohexane diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4
'-And 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomers
Body mixtures are included. Examples of aromatic diisocyanates include 2,4-toluene diisocyanate.
Socyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate
A mixture of anates, 4,4'-, 2,4'- and 2,2'-diphenylmethanediene
Isocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diisocyanate
Mixture of phenylmethane diisocyanates, urethane modified liquid 4,4 'and / or
Or 2,4'-diphenylmethane diisocyanate, 4,4 'diisocyanatodiene
Includes phenylethane- (1,2) and 1,5-naphthalene diisocyanate
It Other examples of suitable diisocyanates include diphenylene 4,4'-diisocyanate.
Nate, 3,3'-dimethoxy-4,4'-diphenylene diisocyanate,
Tylene bis (4-cyclohexyl isocyanate), tetramethylene diisocyanate
Nate, decamethylene diisocyanate, ethylene diisocyanate, ethylide
Diisocyanate, propylene-1,2-diisocyanate, cyclohexyl
-1,2-diisocyanate, m-phenylene diisocyanate, p-phenyl
Diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate
Anate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate,
3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-
Biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene
Diisocyanate, furfuridene diisocyanate, xylene diisocyanate
, Diphenylpropane-4,4'-diisocyanate, bis (2-isocyanato)
Ethyl) fumarate, naphthalene diisocyanate and combinations thereof
, But not limited to these.

Examples of additional diisocyanate compounds include 1,4′-dicyclohexylmethane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, cyclohexylene-1,4-diisocyanate, 4,4
'-Methylenebis (phenylisocyanate), 2,2-diphenylpropane-
4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-diphenyl diisocyanate, azobenzene-4,4'-
Diisocyanate, m- or p-tetramethylxylene diisocyanate, 1
-Chlorobenzene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, 4,6'-xylene diisocyanate, 2,2,4- (2,4,4
-) Trimethylhexamethylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane 4,4
'-Diisocyanate and the like are included.

The preferred diisocyanates used in the examples to demonstrate the effect of the invention were 4,4′-diphenylmethane diisocyanate (MDI) and methylene-bis (4-cyclohexylisocyanate) (H ₁₂ MDI).

[0034]   catalyst   If a catalyst is used, the preferred catalyst is the NCO group of the diisocyanate and the structural component
It promotes the reaction between the hydroxy groups. Examples are known in the art.
, For example, the tertiary amines described in US Pat. No. 6,022,939.
And organometallic compounds. Examples of suitable tertiary amine compounds include triene
Cylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '
-Dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol and diaza
Includes bicyclo (2,2,2) octane and mixtures thereof, suitable organometallic compounds
Examples of products include titanic acid esters, iron compounds, and tin diacetate, tin dioctanoate, and diamine.
Tin dialkyl salts of tin laurate and aliphatic carboxylic acids (eg dibutyltin diacetate)
And dibutyltin dilaurate) and mixtures thereof. Touch
The medium is usually used in an amount of 0.0005 to 0.5 part per 100 parts of the polyhydroxy compound.
To be done.

[0035]   Manufacturing method   The TPU of the present invention was manufactured by the one-shot method. In the example, the hard segment
PTMC polyureta at a concentration of about 10-55% by weight, preferably 20-40% by weight.
Blended in

The isocyanate index, or isocyanate / hydroxy equivalent ratio, depends on the isocyanate and glycol used (often referred to as the chain extender). For thermoset elastomers, the isocyanate index may typically be 0.105-600, or higher. Isocyanate index of the present invention is 0.8 ~ depending on the composition.
It can be 1.04, but is preferably close to about 1.02.

The polyol and glycol (chain extender) are added at 70 to 150 ° C., preferably 95
~ 140 ° C, 100-135 ° C in specific examples. Although it is possible to use slightly higher temperatures, it is generally not recommended to avoid side reactions as is known in the art. The diisocyanate was preheated at the mixing temperature and then added to the polyol and chain extender mixture and all ingredients were mixed vigorously for 5-10 seconds. The mixture was then poured into a preheated (<150 ° C.) Teflon coated mold. The stringing reveals gelation, which usually occurs within about 10 to 20 seconds,
Once gelation had occurred, the mold was placed on a Carver press and the resin was compression molded at high pressure and medium temperature. The pressure is preferably 137.9 to 206.8 MPa (20,
000-30,000 psi) and the preferred temperature is 100-140 ° C.
Suitable pressures may be above said range, as known to those skilled in the art. Then, the polyurethane sheet was post-cured for several hours to several days depending on the temperature in an oven at 90 to 150 ° C, preferably 100 to 140 ° C.

The following examples serve to illustrate specific embodiments of the invention described herein. These examples are illustrative only and should not be construed as limiting the scope of the invention in any way. Those skilled in the art are aware of many modifications that can be made without departing from the spirit of the invention.

(Examples) Table 1 shows materials used in this example. The isocyanate was used as received from the supplier. The NCO% concentration was checked by titration according to the di-n-butylamine method of ASTM D1638-74. The hydroxyl number of the polyol was measured using the standard phthalic anhydride esterification method (ASTM D4273).

[0040]

[Table 1]

[0041]   Example 1   In Example 1, the viscosity of the polyol was examined. Viscosity of PTMC 2000 at room temperature
Desm is due to the high concentration of hard carbonate groups in PTMC 2000.
It was found to be much higher than the open C-200 (Table 2, Figure 1). viscosity
Decreased significantly with temperature. Short hydrocarbon sequence (3 CH_TwoIn order to
The glass transition temperature of PTMC 2000 is −28.5 ° C., and this temperature is 6
CH_TwoTransition temperature of Desmophen C-200 having a group (-58.
It was much higher than 3 ° C).

[0042]

[Table 2]

[0043]   Example 2   In Example 2, the compatibility of the chain extender and the polyol was investigated. PTMC 200
0 and chain extenders (1,4-BD and 1,3-PDO) are compatible with each other in a specific ratio.
Were tested by mixing at different temperatures. A visual observation of the mixture was recorded. versus
Varying the concentration% of chain extender in terpolyol and PTMC 2000 at room temperature
, 70 ° C and 90 ° C. PTMC 2000 has a room temperature to 90 ° C
, 4-butanediol (1,4-BD) and 1,3-propanediol (1,3
-PDO). In this result, the weight of the polyol / chain extender
The quantity ratio corresponds to an elastomer with a hard segment concentration of 22 to 35%. At room temperature
The compatibility of Desmophen C-200 with the chain extender was limited. result
Is shown in Table 3.

[0044]

[Table 3]

[0045]   Example 3   In Example 3, TPU was added at hard segment concentrations of 22, 25, 28 and 35%.
It was manufactured by the one-shot method. Before producing the elastomer, the polyol and
The chain extender was vacuum dried at 70 ° C. for at least 24 hours. Diisocyanate
Used as received from supplier. NCO% is the di-n-butylamine method (AS
Checked by titration according to TM D1638-74). Isocyanate index
(Isocyanate / hydroxyl equivalent ratio) was 1.02. Polyol and
Weigh the chain extender into a plastic cup and heat at 100 ° C or 135 ° C.
I got hot. Benzoyl chloride was added to the mixture of polyol and chain extender. Diiso
The cyanate is preheated at the mixing temperature and then added to the mixture of polyol and chain extender.
All ingredients were mixed vigorously for 5-10 seconds. The mixture is then added to 105
Or poured into a Teflon-coated mold preheated to 135 ° C. (Revealed by string pulling
If gelation occurs, place the mold on the Carver press and load the resin 105 times.
Was compression molded at 135 ° C. and 165.5 MPa (24,000 psi). afterwards
, Place the polyurethane sheet in an oven at 105 or 135 ° C for 24 hours (or
Or 135 ° C. for 20 hours and 150 ° C. for 4 hours). Be sure to post-cure
Is not necessary either. The curing and post-curing conditions in the production of aromatic TPU are shown in Table 4,
Curing and post-curing conditions in the production of aliphatic TPU polyols are shown in Tables 13 and 14.
Show. The polyurethane elastomer was tested one week after manufacture.

[0046]

[Table 4]

[0047]   Example 4   In Example 4, 1,3-PDO extended PTMC 2000 and Desmo
The composition and characteristics of the MDI-based TPU containing phen C-2000 as a main component were tested.
I tried

The data are shown in Tables 5 and 6. Increasing the hard segment concentration from 22% to 35% increased the Shore A hardness of PTMC 2000 TPU from 73 to 91. The hardness of Desmophen C-200 TPU was slightly lower if the hard segment concentration was the same. Generally, TPU tensile strength, modulus and die C tear resistance increased with hard segment concentration as expected. The abrasion resistance of the PTMC 2000 elastomer was very good, higher than that of Desmophen C-200. This is a PT containing many carbonate groups that can form hydrogen bonds.
This may be due to the effect of reinforcing hydrogen bonds in MC 2000 polyurethane.
The wear resistance of PTMC 2000 TPU was equal to or higher than that of PTMO 2000 and TONE polycaprolactone TPU. PTMO 2000 T
Some examples of PU have wear resistance indices of 13 and 20, for example. See Tables 6-A, 17 and 18. The tables also include data on the properties of TPUs based on commercial polyols.

The PTMC TPU exhibited a relatively low compression set (4-7%). This is D
Compression set of esmophen C-200 TPU (14.3 to 23.5%)
Was lower than It is interesting to note that the resilience of 1,3-PDO extended polycarbonate TPU increases with increasing hard segment concentration.

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]   Example 5   In Example 5, PTMC TPU at a hard segment concentration of 22-35%
Produced with 4-BD chain extender and tested for various properties. Table 7
And 8 are shown. PTMC 2000 and Desmophen C-200 TP
U strength properties (tensile strength, stress at 100% and 300% elongation, Young's modulus and
Toughness) and die C tear strength change fairly uniformly with increasing hard segment concentration.
Turned into PTMC-TPU tensile strength compared to Desmophen C-200
However, the elastic modulus was slightly higher in the former case (Figs. 2 and 3).
Due to properties such as elongation at break, elastic modulus and resilience, 1,4-BD extended TP
It can be seen that U is more flexible than that extended with 1,3-PDO. This
Again, the resilience of PTMC TPU increases with increasing hard segment concentration.
Turned out to rise.

[0054]

[Table 8]

[0055]   Example 6   In Example 6, the heat resistance of the elastomer was examined at 70 ° C. for stress-elongation properties.
It was evaluated by. For PTMC 2000 / 1,3-PDO / MDI TPU
Retention of tensile strength is Desmophen C-200 / 1,3-PDO / MDI
It was found to be slightly higher than TPU (see FIG. 4). Defeat of PTMC 2000
The elongation at break increased significantly upon heating and the elastic modulus decreased (see Table 5). Desmo
The heat resistance of phen C-200 / 1,4-BD / MDI TPU was low (Table
8). In the case of PTMC TPU, the coefficient of thermal expansion measured by TMA is Desmop
It was found to be low compared to hen C-200 TPU (see Table 9). TMA
The softening temperature of TPU measured by PTMC 2000 is 160 to 209 ° C,
For Desmophen C-200 Polyurethane at 160-175 ° C
there were. The softening temperature of Desmophen C-200 is influenced by the chain extender.
I hardly received it.

[0056]

[Table 9]

[0057]   Example 7   In Example 7, the morphology was tested. The glass transition temperature of PTMC TPU is about 0 ℃
Then, when measured by DMA, the shift was about 10 ° C. Relatively high T_gThe above-mentioned
Polyurethane is an elastic plastic material that has very good elasticity above room temperature.
Is defined. The glass transition temperature of Desmophen C-200 TPU is about 3
It was 0 ° C lower. Morphology was also examined by FTIR spectroscopy. Elastomer FTIR
The vector showed a band typical of polycarbonate aromatic polyurethane. You
Nozawa, 3300-3400 cm^-1-NH (free and bound), 2900-2
970 cm^-1To CH_Two, 1740 to 1759 cm^-1Carbonate and bond
C = O in the urethane group, 1760 cm^-1To C = O free urethane group, 1600c
m^-1To aromatic group, 1033cm^-1Shows -COC in the ether group.
Absorbance ratio 1705 cm^-1/ 1745 cm^-1Is probably the proportion of unbonded urethane groups
Increases with increasing hard segment concentration. The ratio is PTMC T
It turned out to be higher in PU. Hydrogen bonds in polycarbonate polyurethane
Is formed by crosslinking between urethane groups and between carbonate groups and urethane groups.
It

[0058]

[Table 10]

[0059]   Example 8   In Example 8, the composition containing PDO / MDI was tested for water resistance. Water resistance is
Measure the weight increase and change in stress-elongation property when immersed in water at 70 ° C for 2 weeks.
It was evaluated by The results are shown in Tables 10 and 11 and FIGS. PTMC
The weight increase of TPU is 1.2-1.6%, Desmophen C-200
Was low (0.8-1%). These results are for PTMC 2000 (
8 to 57% depending on the hard segment concentration, Desmophen C-200
In the case of, the correlation is well correlated with the change of tensile strength of 3.6 to 33.5%. Des
Mophen C-200 has good water resistance because it has more hydrophobic structures (6
-CH_TwoGroup) is present.

Relative transparency was investigated by measuring the light transmission (%) in the visible range of 474-630 nanometers. Clarity decreased with increasing hard segment concentration. PTMC 2000 TPU is Desmo at any hard segment concentration
It showed significantly higher transparency than phen C-200. This may be due to the low order structure of the PTMC skeleton or the high degree of phase mixing of the flexible and hard segments.

[0061]

[Table 11]

[0062]

[Table 12]

[0063]   Example 9   In Example 9, the chemical resistance of TPU was oil (100% neutral paraffin oil), Fis.
her Brand 19, ethylene glycol, dilute acid (10% H_TwoSO_FourOver
And 10% HCl) and various media including sodium hydroxide. Table of results
12 and 7 are shown. The weight increase in hydraulic oil is low, in inorganic acids it is high, especially P
High for TMC TPU. 35% increase in weight in sodium hydroxide
Relatively low except for Desmophen C-200 with hard segment concentration
. Unexpectedly, the weight gain in ethylene glycol was
It was much lower for PTMC than for C-200 TPU. as a whole,
The resistance of TPU in this medium was good. As a reference, poly (oxytetrame
Table 12-A shows the resistance of TPU containing (ethylene) glycol as a main component.

[0064]

[Table 13]

[0065]

[Table 14]

[0066]   Example 10   In Example 10, alicyclic diisocyanate H₁₂MDI and PTMC 200
A 0-based TPU was cured. The curing conditions are shown in Tables 13 and 14. Of each table
In the first row, SPH-25 to SPH-35 have a hard segment concentration of 25 to 35%.
PTMC 2000 / 1,3-PDO / H₁₂Corresponds to MDI. SBH-25
-SBH-35 is PTMC 2000/1 with a hard segment concentration of 25-35%.
, 4-BD / H₁₂Corresponds to MDI.

The tensile strength increased with the hard segment concentration, but showed a moderately higher value for the 1,3-PDO chain extender than the 1,4-BD chain extender. For both MDI and H ₁₂ MDI, PTMC 2000 TPU showed better properties with 1,3-PDO chain extender than 1,4-BD chain extender. H ₁₂ M
Note that DI TPU was cured at a lower temperature than MDI TPU due to its lower green strength.

The glass transition temperature was measured by a differential scanning calorimeter and a dynamic mechanical method. The DSC glass transition temperature of H ₁₂ MDI TPU was slightly lower than 0 ° C. and lower than that of TPU containing MDI as a main component. This indicates low interaction between the flexible segment and H ₁₂ MDI. Softening temperature of H ₁₂ MDI was usually one hundred seventy-five to one hundred ninety-three ° C.. The 1,3-PDO extended TPU was transparent when the hard segment concentration was 25%, and was translucent when the hard segment concentration was 28 to 35%. The 1,4-BD extended TPU was translucent at a hard segment concentration of 25% and cloudy at higher concentrations. As a reference, TP containing H ₁₂ MDI / PTMO 2000 / 1,4-BD as a main component
Various characteristics of U are shown in Table 13-A.

The weight change of SPH-TPU when immersed in water at 70 ° C. for 2 weeks was 1.2 to 1.
73%, which was equivalent to MDI-TPU (see Table 15).

Hydraulic oil, ethylene glycol, 10% HCl, 10% H ₂ SO ₄ and 10
% Table 1 the measured resistance by increase in weight of _H 12 MDI-TPU in a NaOH
6 shows. The oil resistance was excellent (no weight increase). The weight gain in acids, sodium hydroxide and especially ethylene glycol was high.

[0071]

[Table 15]

[0072]

[Table 16]

[0073]

[Table 17]

[0074]

[Table 18]

[0075]

[Table 19]

[0076]

[Table 20]

[0077]

[Table 21]

[Brief description of drawings]

[Figure 1]   It is a graph which shows the viscosity of polycarbonate polyol.

FIG. 2 is a bar graph showing stress at 100% elongation of TPU containing 1,4-butanediol (1,4-BD) as a main component.

FIG. 3 is a bar graph showing the stress at a 300% elongation of TPU containing 1,4-BD as a main component.

FIG. 4 is a bar graph showing retention of tensile strength of TPU containing 1,3-propanediol (1,3-PDO) as a main component.

[Figure 5]   It is a bar graph which shows the weight change after immersion in 70 ° C water for 2 weeks.

[Figure 6]   It is a bar graph which shows the tensile strength of the initial stage and after dipping in water of 70 ° C for 2 weeks.

[Figure 7]   3 is a bar graph showing chemical resistance after immersion for 1 week.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE, TR), OA (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, B Z, CA, CH, CN, CR, CU, CZ, DE, DK , DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, J P, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, R O, RU, SD, SE, SG, SI, SK, SL, TJ , TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Fritschyu, Kurt Challes             United States, Michigan 48138, GLO             Suh Eal, Park Lane 17986 (72) Inventor Gwin, David Elitsk             Texas, 77072-1708, USA             Hyeuston, South Briar By             Woo 6502 (72) Inventor Sendaji Yervik, Aisa             Toro, 48098, Michigan, United States             Lee Atkins Road 6284 F-term (reference) 4J034 BA05 BA08 CA01 CA04 CB03                       CB07 CC01 CC03 CC11 CC22                       CC23 CC26 DA01 DB04 DF02                       HA01 HA07 HA11 KD11 KD12                       QB08 QB14

Claims (10)

[Claims] 1. A hard segment defined as a) a poly (trimethylene carbonate) diol (PTMC diol) as a soft segment, b) a diisocyanate, and c) a total portion of glycol-reactive diisocyanate and unreacted glycol. A thermoplastic polyurethane elastomer (TPU) composition comprising at least one glycol that reacts with said diisocyanate to form 10-55% by weight of the product. 2. The molecular weight of poly (trimethylene carbonate) diol is 30.
The composition according to claim 1, wherein the composition is 0 to 6000. 3. The molecular weight of poly (trimethylene carbonate) diol is 10.
The composition according to claim 2, wherein the composition is from 00 to 3000. 4. The functionality of the poly (trimethylene carbonate) diol is about 2.
The composition according to any one of claims 1 to 3, wherein: 5. Composition according to any one of claims 1 to 4, characterized in that the hard segments are mixed in an amount of 10 to 50% concentration. 6. A composition according to claim 5, characterized in that the hard segments are mixed in an amount of 20-40% strength. 7. A glycol according to claim 1, characterized in that the glycol in the hard segment is selected from aliphatic, cycloaliphatic, aralkyl and aromatic glycols.
The composition according to any one of item 6. 8. The glycol is ethylene glycol, propylene glycol,
1,3-propanediol, 2-methyl-1,3-propanediol, 2,4-
Dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3
-Propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2
-Ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl- 1,6-hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1
Composition according to claim 7, characterized in that it is selected from 1,3-cyclobutanediol, p-xylenediol and mixtures thereof. 9. Composition according to claim 8, characterized in that the glycol is selected from 1,3-propanediol, 1,4-butanediol and mixtures thereof. 10. Composition according to any one of claims 1 to 9, characterized in that the diisocyanate is selected from aromatic, aliphatic or cycloaliphatic diisocyanates.