JP3301528B2 - Method for preparing amorphous polymer chains in elastomers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for preparing an amorphous polymer chain in an elastomer by a novel method different from the conventional one, and further prepares an elastomer having rubber elasticity and excellent mechanical strength. About the method.

[0002]

BACKGROUND OF THE INVENTION Generally, elastomer (rubber elastic) is
It refers to a substance obtained by chemically or physically bonding a part of a linear polymer substance (raw rubber: raw rubber) in which molecular rotational movement is active at room temperature. Representative elastomers include those obtained by crosslinking a part of natural rubber with sulfur or peroxide. Such an elastomer derived from natural rubber is a polymer compound in which monomer components are arranged in a stereoregular state, and is in an amorphous state in an ordinary state, but is in an amorphous state in an excessively deformed state. Because it exhibits oriented crystallinity, it is an ideal elastomer that exhibits good wear resistance and strength.
Conventionally, various elastomers using synthetic amorphous polymer chains have been designed or prepared.

The following are examples of such conventional amorphous polymer chains. First, isoprene rubber (IR), butadiene rubber (B
R), chloroprene rubber (CR) and the like, and the microstructure of these polymers greatly affects the crystallinity of these polymers.

[0004] Here, IR is a polymer of isoprene, which is a polymerized unit of natural rubber (NR), and is selectively cis-
By increasing the number of 1,4 bonds to the same level as that of natural rubber, high physical properties close to those of natural rubber are obtained. BR
It is known that crystallinity and the like can be controlled by highly controlling a microstructure such as cis-1,4, trans-1,4,1,2 or 1,3 addition. Also, C
R is a crystalline polymer mainly composed of a trans-1,4 structure.

[0005] Second, styrene-butadiene rubber (SBR), ethylene propylene rubber (EP
R) and other monomers that form a homopolymer having a low glass transition temperature (Tg) (for example,
(Butadiene, ethylene, etc.) as one of the copolymerized components, and is subjected to random polymerization to make it amorphous (amorphous).

A third example is an alternating copolymer such as tetrafluoroethylene-propylene rubber, which is made amorphous by changing the length of the unit structure constituting the polymer by the alternating copolymerization. .

A fourth example is a method of grafting or block copolymers such as block SBR, which comprises two units, a rubber component and a resin component, which are arranged in a graft or block form and made amorphous. It is.

A fifth method is a method for preparing a chemically modified polymer such as chlorosulfonated polyethylene rubber (CSM) and chlorinated polyethylene (CM).
Is obtained by chemically modifying a crystalline homopolymer having a low crystallinity to make it non-crystalline or amorphous.

A sixth example is a liquid or low-crystalline oligomer having a reactive group at its molecular terminal, and a polymer having a high molecular weight obtained by using a chain extender that reacts with this terminal. It is typically used for kneaded polyurethane.

As described above, conventionally, in order to prepare a good amorphous polymer chain having active molecular mobility,
It is necessary to reduce the intermolecular force and reduce the steric hindrance of molecular rotation, and the above-mentioned amorphous polymer chains have been designed or prepared. In other words, the conventional amorphous polymer chain designing method is a method of arranging the double bonds of the polymer chain in a stereoregular manner, and when a homopolymer is used, a plurality of monomers exhibiting crystallinity are symmetric. A plurality of monomers having different properties such as properties and structural lengths are randomly copolymerized or alternately copolymerized to reduce the crystallinity to be amorphous, and a plurality of monomers containing at least one monomer to be amorphized. A method in which a monomer is graft-copolymerized or block-copolymerized to form an amorphous state as a whole, a method in which a homopolymer having crystallinity is chemically modified to be made amorphous, and a method in which an amorphous oligomer is made to have a high molecular weight. And so on. Amorphous polymer chains combining these features are also known.

For example, in the CR, for example, in order to meet the demand for continuous use at low temperatures, a CR whose crystallinity is reduced by copolymerizing another monomer is used ( German Offenlegungsschrift 2,23
No. 5,811).

[0012] With the recent diversification of industry, various elastomers having various functions have been demanded, but it has become impossible to cope with only existing elastomers.

Although the appearance of a high-performance elastomer having characteristics considered to be contradictory in the past has been demanded, the above-mentioned conventional method cannot easily cope with the problem. That is, for example, in order to prepare a reversible polymer chain in which crystallization occurs by extension and becomes amorphous when the extension is released, it is necessary to prepare an amorphous polymer chain having structural regularity. However, it is very difficult to perform such fine adjustment as desired by the above-described conventional method.

For example, such a high-performance elastomer is
It is said that it can be prepared by controlling the stereoregularity, copolymer composition, and molecular weight distribution collectively using a catalyst such as a metallocene system, but since the monomer is limited to an olefin system, the desired It is difficult to freely prepare high-performance elastomers having properties.

[0015] In view of such circumstances, the present invention converts an elastomer having a high performance or a high function, which has heretofore been difficult by an unconventional method, into a simple process such as ring-opening polymerization, polyaddition and polycondensation. It is an object of the present invention to provide a method for preparing an amorphous polymer chain which can be industrially produced in combination.

[0016]

According to a first aspect of the present invention, a predetermined number of monomer units are provided.
With repeating units having molecular weight distribution of
Selecting an oligomer; and
A compound that reacts with the terminus.
Selecting a binding unit that inhibits the crystallinity of
And combining these steps to form a binding unit that inhibits the crystallinity of the oligomer.
Alternatingly linked, the oligomer is reversibly switched between an elastic state in which the crystallinity of the oligomer is restricted under normal use conditions and rubber elasticity is exhibited, and an oriented crystallization state in which the crystallinity is developed by excessive deformation. And a method for preparing an amorphous polymer chain in an elastomer.

[0017]

The second aspect of the present invention is directed to the first aspect.
And a method for preparing an amorphous polymer chain in an elastomer , wherein the linking is by polyaddition or polycondensation.

In a third aspect of the present invention , in the first or second aspect, the glass transition temperature of the amorphous polymer chain is-
A method for preparing an amorphous polymer chain in an elastomer, wherein the temperature is 20 ° C. or lower.

[0020]

[0021] A fourth aspect of the present invention, in the first to third one aspect, while the crystalline polyol to make both ends with hydroxyl groups the crystalline oligomer, the crystalline oligo
Urethane bond Yoo derived the coupling unit to the diisocyanate compound as a diisocyanate reacted with Ma
A method for preparing an amorphous polymer chain in an elastomer characterized by being knitted .

A fifth aspect of the present invention is the method according to any one of the first to fourth aspects, wherein the cyclic monomer is formed by chain-opening a monomer unit derived from the cyclic monomer by ring-opening addition to the initiator. The crystal having a unit
A method for preparing an amorphous polymer chain in an elastomer, wherein a hydrophilic oligomer is formed and a part of the binding unit is composed of the initiator.

According to a sixth aspect of the present invention, in the fifth aspect, the repeating unit of the chain of the monomer units is ε.
-The crystalline oligomer is represented by the following formula as caprolactone, the average value of the caprolactone chain in the poly-ε-caprolactone diol is a predetermined number, and the caprolactone diol portion of the poly-ε-caprolactone diol A method for preparing an amorphous polymer chain in an elastomer, wherein the molecular weight distribution Mw / Mn is 1.0 to 1.5.

[0024]

Embedded image (Here, [] indicates a caprolactone chain portion, and m
And n indicate the number of chains, and R ₁ is a polymerization initiator R ₁ (O
H) derived from ₂ )

A seventh aspect of the present invention is the method for preparing an amorphous polymer chain in an elastomer according to the sixth aspect, wherein the molecular weight distribution Mw / Mn is 1.0 to 1.3. .

An eighth aspect of the present invention is the composition according to the sixth or seventh aspect, wherein the polymerization initiator R ₁ (OH) ₂ of the poly-ε-caprolactone diol is a linear glycol having 2 to 12 carbon atoms. Neopentyl glycol, 3-methyl-
Diols having a side chain having 12 or less carbon atoms, such as 1,5-pentanediol; and 3-allyloxy-1,2
-At least one selected from the group consisting of diols having an unsaturated group having 12 or less carbon atoms, such as propanediol, wherein the average value of the caprolactone chain is 3 to 6
The method for producing an amorphous polymer chain in an elastomer, wherein

The ninth aspect of the present invention is the eighth aspect, wherein the poly-ε-caprolactone diol polymerization initiator R ₁ (OH) ₂ is a straight-chain glycol having 2 to 12 carbon atoms and methyl A method for producing an amorphous polymer chain in an elastomer, characterized in that it is at least one selected from the group consisting of groups not containing side chains such as groups.

In a tenth aspect of the present invention, in the sixth or seventh aspect, the polymerization initiator R ₁ (OH) ₂ of the poly-ε-caprolactone diol is 1,4-bis (hydroxyethoxy) benzene And at least one selected from the group consisting of diols containing an aromatic ring such as para-xylene glycol, alicyclic diols such as cyclohexanediol and cyclohexanedimethanol, and the average value of the caprolactone chain is 4 to 8. A method for producing an amorphous polymer chain in an elastomer, which is characterized in that: An eleventh aspect of the present invention is the method according to any one of the fifth to tenth aspects, wherein the polyol is the poly-ε
-A method for preparing an amorphous polymer chain in an elastomer, comprising a chain extender in addition to a long-chain diol containing a caprolactone-based diol.

In a twelfth aspect of the present invention, in any one of the fourth to eleventh aspects, the glass transition temperature Tg is -20 ° C.
A method for preparing an amorphous polymer chain in an elastomer characterized by the following.

A thirteenth aspect of the present invention is the composition according to any one of the fourth to twelfth aspects, wherein the diisocyanate is 2,6.
-Toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI) and 3,3-dimethyldiphenyl-4,4'-diisocyanate (TODI) )
A method for preparing an amorphous polymer chain in an elastomer, wherein the method is at least one selected from the group consisting of:

In a fourteenth aspect of the present invention, the poly-ε-caprolactone diol according to any one of the fourth to thirteenth aspects is characterized in that
The present invention relates to a method for preparing an amorphous polymer chain in an elastomer, which is produced under a reaction condition of not more than ° C.

[0032]

Embedded image (Where R ₂ represents hydrogen, an alkyl group or an aryl group, X represents a hydroxyl group, an alkoxide group or a halogen other than fluorine)

According to a fifteenth aspect of the present invention, in any one of the first to third aspects, the crystalline oligomer is a diol, while the compound that reacts with the crystalline oligomer is a diisocyanate. A method for preparing an amorphous polymer chain in an elastomer, comprising designing a soft segment of polyurethane and preparing the above cast or thermoplastic polyurethane with the soft segment and the hard segment.

According to a sixteenth aspect of the present invention, in any one of the first to third aspects, the crystalline oligomer is a dicarboxylic acid, the compound reacting with the oligomer is a diamine, and the bonding unit is an amide bond. And a method for preparing an amorphous polymer chain in an elastomer.

The preparation method of the present invention is completely different from the conventional design concept of controlling the stereoregularity of a polymer chain, and an oligomer polymer chain is formed of a repeating unit and a bonding unit for bonding the same. By controlling the number of repeating units and the number of repeating units and the molecular weight distribution of repeating units, it is possible to design an amorphous polymer chain using a monomer with a composition that was conventionally too strong to be used because it was too crystalline. Can be done. Moreover, since the preparation method of the present invention can be achieved by a very simple method such as ring-opening polymerization and polyaddition or polycondensation, in industrial production, the range of material selection can be greatly improved, and the degree of freedom in design can be greatly increased. Can be improved.

More specifically, by controlling the number of repeating units and the molecular weight distribution of the repeating unit of the crystalline oligomer, the crystallization of the oligomer is inhibited by the influence of the binding unit that binds to the oligomer. It is also possible to use a monomer having a composition which has heretofore been unusable as having too high a property. That is, according to the method of the present invention, a crystalline oligomer having a high melting point, which could not be easily incorporated into an amorphous polymer chain in the past, can also be incorporated.

Here, the crystalline oligomer refers to an oligomer having a melting point, preferably an oligomer having a melting point of 20 ° C. or more, more preferably 30 ° C. or more.

The monomer unit is composed of a single monomer or a plurality of monomers, and a repeating unit is formed from a predetermined number of chains of the monomer unit. In general, the repeating unit including a terminal includes an oligomer. Becomes Further, the oligomer may have a structure in which a chain of the monomer units is bonded to both ends of the polymerization initiator.
Specifically, this is the case where the oligomer is composed of the poly-ε-caprolactone polyol represented by the general formula (I) described above. In this case, the polymerization initiator is R as described above.
₁ (OH) ₂ and a repeating unit represented by the general formula (I)
In [], wherein m and n in the general formula (I) are the number of chains.

The binding unit may be arranged at at least one end of the repeating unit. Preferably, the binding unit is arranged at both ends of the repeating unit so as to inhibit crystallization of the oligomer. Good. In addition, the amorphous polymer chain thus prepared has a glass transition temperature of -2 to be used as an elastomer.
It must be below 0 ° C.

Further, according to the method of the present invention, by controlling the number of monomer units of the amorphous polymer chain and the molecular weight distribution of the repeating units, the crystallinity and the amorphousness thereof are controlled. It is possible to prepare a high-performance or high-performance elastomer in which crystallization is inhibited and crystallinity is developed in an excessively deformed state.

For example, regarding polyurethane,
A polyurethane using a polycaprolactone polyol having a narrow molecular weight distribution is disclosed in, for example, Japanese Patent Publication No. 63-39007. However, the present invention is to develop a polyurethane having an excellent elastic recovery force as compared with a conventional product. Further, polyols having a narrow molecular weight distribution are described in, for example, Japanese Patent Publication No. 3-562.
No. 51, Japanese Patent Application Laid-Open No. 7-292083, and Japanese Patent Application Laid-Open No. 63-196623 also disclose a novel polyol which has never existed before.

That is, conventionally, there is no knowledge that the crystallinity of a polyol can be controlled by controlling the molecular weight and molecular weight distribution of the polyol within an appropriate range and reacting the polyol with a diisocyanate.

According to the present invention, with respect to the polyol, if a molecule having a molecular weight equal to or more than a predetermined molecular weight is contained, the entire portion thereof is crystallized, and if the number of molecules having a molecular weight lower than the predetermined molecular weight increases, the glass transition temperature Tg becomes low. However, it is based on the finding that desired rubbery elasticity cannot be obtained.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The preparation method of the present invention is carried out by controlling the molecular weight distribution of an oligomer having crystallinity to be small and designing the oligomer to be connected via an appropriate bond. You. In order to regularly arrange and link these oligomers and binding units,
It is desirable to design the molecular structure formed by the polyaddition / polycondensation reaction.

As a specific example, for example, there can be mentioned an example in which a polyol is used as an oligomer and a urethane binding unit is used as a binding unit. Here, examples of the polyol include those not conventionally used for such applications because of the crystallinity, such as poly-ε-caprolactone diol. And it is designed so that when the molecular weight distribution is controlled and the range thereof is reduced to react with diisocyanate, crystallization is inhibited by the polyurethane binding unit derived from diisocyanate. For example, when a polyol having a poly-ε-caprolactone diol as a main component represented by the above formula (I) is used, the average value of the caprolactone chain in the poly-ε-caprolactone diol is 3 to 6, and If the molecular weight distribution Mw / Mn of the caprolactone chain portion of the -ε-caprolactone diol is 1.0 to 1.5, crystallization of the caprolactone chain portion is inhibited. In addition, when the average value of the caprolactone chain is 7 or more, a portion where crystallization is not inhibited by the urethane binding unit occurs, and when the caprolactone chain is 2 or less, the glass transition temperature exceeds -20 ° C, and the caprolactone chain is used as an elastomer. Is not preferred.

Here, the poly-ε-caprolactone diol is synthesized by the reaction of ε-caprolactone monomer and a polymerization initiator.
Shown is one using ₁ (OH) ₂ .

The polymerization initiator is not particularly limited as long as it has an active hydrogen and forms a diol after ring-opening polymerization, and in addition to diols having an active hydrogen,
Diamines and the like can also be used.

Further, such an initiator affects the crystallinity of the caprolactone chain portion as described above. Therefore, when R ₁ is, for example, a linear hydrocarbon, it is necessary to control the average value of the above-mentioned caprolactone chain to 3 to 6, but R ₁ is, for example, a steric hindrance such as an aromatic ring or an aliphatic ring. In this case, the average value of the caprolactone chain may be controlled to 4 to 8 when the initiator has a large effect on the crystallinity of the caprolactone chain portion. That is,
In the present invention, the average value of the caprolactone chain is appropriately controlled to a predetermined value according to the type of the polymerization initiator.

Examples of the short-chain initiator that can be used in the present invention include linear glycols having 2 to 12 main chain elements such as ethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol. Diols having a side chain having 12 or less carbon atoms such as neopentyl glycol and 3-methyl-1,5 pentanediol; having an unsaturated group having 12 or less carbon atoms such as 3-allyloxy-1,2-propanediol. Diols; and diols having 20 or less carbon atoms containing an aromatic ring such as 1,4-bis (hydroxyethoxy) benzene and para-xylene glycol; alicyclic diols such as cyclohexanediol and cyclohexanedimethanol; Can be mentioned.
Of course, these short-chain initiators may be used as a mixture of two or more.

In order to form the poly-ε-caprolactone diol used in the present invention, it is important to select a catalyst in addition to ε-caprolactone and a polymerization initiator. As the catalyst capable of restricting the molecular weight distribution narrowly, it is preferable to use a metal compound catalyst containing a halogen or an organic acid group, for example, chlorine, bromine, stannous halide such as iodine, or the above formula (II) The tin catalyst shown can be exemplified.

The poly-ε-caprolactone suitable for use in the present invention, whose molecular weight distribution is narrowly restricted, is preferably a tin-based catalyst represented by the above general formula (II), for example, monobutyltin oxide or fluorine. It is preferably produced by polymerization using a tin halide to be removed, preferably under a low temperature condition of 130 ° C. or lower. When monobutyltin oxide or tin halide other than fluorine is used as described above, a monodispersed poly-ε-caprolactone having a molecular weight distribution of 1.0 to 1.3 can be obtained even at a temperature of 100 to 200 ° C. With no progress of crystallization, crystallization does not occur, and it can be carried out without a solvent. In contrast,
For example, the technology disclosed in Japanese Patent Application Laid-Open No. 63-196623 described above is based on a conventional reaction temperature of 100 to 200 ° C., in which a lactone is subjected to ring-opening polymerization at 100 ° C. or lower using an inorganic acid catalyst as a catalyst to obtain a molecular weight A very monodispersed lactone polymer having a distribution Mw / Mn of 1.0 to 1.2 is obtained. In such bulk polymerization at a relatively low temperature, crystallization is likely to occur as the polymerization proceeds, and it is said that the reaction is preferably carried out in an inert organic solvent such as benzene or toluene. A step of removing the solvent from the reaction completed solution or a step of recovering the solvent is required, which may be a problem in industrialization.

In the present invention, as a main component of the polyol,
Although the above-mentioned specific poly-ε-caprolactone diol which is a long-chain polyol is used, other generally used long-chain polyols and chain extenders can be used as long as the object of the present invention is not impaired. As a generally used long-chain polyol, any of a polyester-based polyol and a polyether-based polyol may be used, or a blend or a partially modified one thereof may be used. As the chain extender, for example, ethylene glycol, thiodiethanol,
Linear glycols having 2 to 12 main chain elements such as propylene glycol and butylene glycol; diols having a side chain having 12 or less carbon atoms such as neopentyl glycol and 3-methyl-1,5-pentanediol; 3 12 carbon atoms such as allyloxy-1,2-propanediol
Diols having the following unsaturated groups; and 1,4-
Examples thereof include diols having an aromatic ring such as bis (hydroxyethoxy) benzene and para-xylene glycol having 20 or less carbon atoms and hydrogenated products thereof. Further, triols such as trimethylol, Stearyl alcohol, hydroxyethyl acrylate and the like can also be used.

When the polyurethane obtained by the method of the present invention is crosslinked with sulfur, a compound having an unsaturated bond is used as a part of an initiator or a chain extender according to a conventional method.

Such a diol can be reacted with a suitable diisocyanate to form an amorphous polymer chain. Such an amorphous polymer chain can be a kneaded polyurethane, which can be crosslinked with sulfur, a peroxide, a metal salt, or the like, alone or by incorporating an appropriate crosslinking site, to obtain a kneaded polyurethane.

In this case, crystallization is inhibited in a normal deformed state and crystallinity is developed in an excessively deformed state, so that mechanical strength and wear resistance are improved. And excellent polyurethane.

The adjusting method of the present invention described above has a possibility of using a wider range of materials as compared with the conventional design concept, and therefore has general versatility. Conventionally, the crystallinity is too strong. It is possible to design using an oligomer that was not targeted for the elastomer design, and the design flexibility is greatly improved.

Further, according to the preparation method of the present invention, the oligomer has an elastic state in which the crystallinity of the oligomer is restricted under normal use conditions and shows rubber elasticity, and the oligomer has a crystallinity due to excessive deformation. It is also possible to finely adjust the crystallinity in order to reversibly have the oriented crystallized state that appears. One factor for such fine tuning is, for example, the selection of the above-mentioned initiator R ₁ in poly-ε-caprolactone. In selecting R ₁ of this initiator, in order to develop reversible crystallinity,
It is desirable to use a compound containing a straight-chain glycol having 2 to 6 carbon atoms or an aromatic ring or an alicyclic ring and not containing an alkyl side chain such as a methyl group. In particular, among cyclic compounds,
Those in which a chain unit with a lactone is directly or indirectly bonded to the 1,4-position show ideal reversibility, for example, para-xylene glycol, 1,4-bis (hydroxyethoxy) benzene (BHEB), etc. Can be mentioned.

The amorphous polymer chains thus designed by the method of the present invention may be crosslinked with sulfur, a peroxide, a metal salt, etc., alone or by incorporating an appropriate crosslinking site, to form an elastomer. Can be.

The amorphous polymer chain designed by the method of the present invention can be used not only as a raw rubber as described above but also as a soft segment of a thermoplastic elastomer. Further, a cast or thermoplastic polyurethane elastomer can be used. The cast or thermoplastic polyurethane elastomer can be prepared using the soft segment and the hard segment.

[0060]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on an embodiment.

This embodiment describes an example of preparing an amorphous polymer chain of a kneading type polyurethane elastomer.

First, ε-caprolactone, which is used to obtain a cast-type high-strength polyurethane, was selected as a monomer unit of a repeating unit constituting an amorphous polymer chain. This ε-caprolactone is
Ring-opening polymerization using a polymerization initiator R ₁ (OH) ₂ and a catalyst forms a crystalline oligomer having a chain of ε-caprolactone on both sides of R ₁ and a hydroxyl group at a terminal. The oligomer is reacted with diisocyanate to form an amorphous polymer chain. In this amorphous polymer chain, the crystallinity of a repeating unit composed of a chain of ε-caprolactone is inhibited by a polyurethane binding unit derived from diisocyanate and R ₁ derived from a polymerization initiator.

Therefore, the physical properties of various kneaded polyurethanes were investigated according to the following procedures.

(Survey for Selection of Number of Chains)
Poly-ε-caprolactone in which ethylene glycol is selected as an initiator, the molecular weight distribution is fixed to about 1.4 and 2.2, and the average number of caprolactone chains is changed in the range of 2.5 to 8.5. A system diol was prepared.

Here, the group of samples 1 to 7 (referred to as group A) has a narrow molecular weight distribution of about 1.4, and the group of samples 8 to 14 (referred to as group B) has a molecular weight distribution of 2.2. To the extent of conventional and normal ranges. Table 1 shows the amount of catalyst used and the reaction temperature, the designed and calculated values of the number of ε-caprolactone chains, the designed and measured average molecular weights, and the molecular weight distribution (Mw / Mn) for each reaction.

The average molecular weight is a value obtained by measuring the hydroxyl value of a polyol according to 6.4 of JIS K1557 and calculating the following equation.

Molecular weight = 56.1 × N × 1000 / hydroxyl value N: Number of functional groups of initiator The molecular weight distribution was determined by gel permeation chromatography (GPC) under the following conditions.

Apparatus: LC-3A, Shimadzu Corporation Solvent: Tetrahydrofuran 1 ml / min Temperature: 50 ° C. Column: Shodex KF801, 1 KF8025, 1 KF804, 1 Detector: RID-6A, Shimadzu Corporation

[0069]

[Table 1]

Each of the poly-ε-caprolactone diols produced as described above was reacted with an equimolar polyisocyanate (MDI) at 100 ° C. for 5 hours to obtain various kneaded polyurethanes.

To determine the properties of these kneaded polyurethanes as amorphous polymer chains, the glass transition point Tg of each kneaded polyurethane and the flexibility in low-temperature storage were investigated. Here, the stability in low-temperature storage was determined from the flexibility when left at −15 ° C., 5 ° C., and 25 ° C. for 3 days. Table 2 shows the results.

As a result, in both the group A having a narrow molecular weight distribution of poly-ε-caprolactone polyol and the group B having a wide molecular weight distribution, the crystallinity increases as the average number of ε-caprolactone chains increases. I knew it was there. Further, it has been clarified that the temperature range in which the amorphous state can be maintained is wider in Group A where the molecular weight distribution is narrower than in Group B.

[0073]

[Table 2]

Further, each kneaded polyurethane 1
The crosslinking agent dicumyl peroxide (manufactured by NOF Corporation; Parkmill D (trade name)) 1.5
After adding the parts by weight and kneading with an open roll,
Press molding was performed at 0 ° C. for 20 minutes to obtain various crosslinked elastomers.

Regarding various crosslinked elastomers, JIS K
Hardness (Hs: JIS A scale) according to 6253, Rebound resilience (Rb:%), JIS K6251 according to JIS K6255 (based on ISO4662)
(Based on ISO37), tensile strength (Tb: MP
a) and elongation (Eb:%), and JIS K625
2 (according to ISO34), tear strength (Tr: N /
mm). The initial hardness was measured after a heat treatment at 60 ° C. for 30 minutes and a standing at 23 ° C. for 3 hours. Table 3 shows the results. Further, the hardness after being left at each temperature for 3 days was measured. The results are also shown in Table 3. Further, for Samples 3, 4, 9, and 10, -20C to 60C.
The temperature dependence of the rebound resilience at ° C. was measured. The result is shown in FIG.

Further, a phenomenon in which the hardness after crystallization of each crosslinked elastomer was allowed to stand for 3 days at each temperature to increase the hardness (cold hardening) was observed. It was found that those using poly-ε-caprolactone having a molecular weight of 1500 (average number of chains: 6) showed an increase in hardness even at room temperature. Further, even if the average number of chains is reduced to 3 or less, the crystallinity is not observed in the elastomer using the one having 3 or less, but the temperature dependence of the physical properties becomes large even at around normal temperature, causing a problem as the elastomer. On the other hand, it was found that when poly-ε-caprolactone having a narrow molecular weight distribution was used, an elastomer having a low temperature dependency was obtained while preventing an increase in hardness.

From these facts, it is considered that the increase in hardness due to crystallization depends on the number of lactone monomer chains. Conversely, if the number of chains increases more than a predetermined value, the crystallinity increases, and the elastomer as an amorphous polymer chain in the elastomer is increased. It is considered that a defect occurs. Further, when the average value of the chains is less than a predetermined number (for example, less than 3), the concentration of urethane groups in the amorphous polymer chain increases, so that the glass transition point becomes high, and a problem occurs in temperature dependency. Therefore, in order to obtain a practically low glass transition point (for example, −20 ° C. or less) as an elastomer while suppressing crystallization, it is useful to regulate the distribution of ε-caprolactone chains to a very high degree. Furthermore, based on the finding that it is the ε-caprolactone chain that is to be crystallized, fine adjustment of crystallinity, which has been difficult in the past, was achieved by selectively arranging molecules that regulate crystallization on both sides of the lactone chain. It is considered possible.

[0078]

[Table 3]

(Investigation for Selection of Molecular Weight Distribution) As shown in Table 4, the effect of changing the molecular weight distribution while fixing the number of caprolactone chains was investigated.

Here, group C of samples 15 to 19
Is obtained by changing the molecular weight distribution between 1.15 and 2.13 with the number of ε-caprolactone average chains being 6,
Group D of Samples 20 to 24 has a molecular weight distribution of 1.18 to 5 with the average number of ε-caprolactone chains being 5.
It is changed between 2.21.

Table 5 shows the amount of catalyst used and the reaction temperature, the designed and calculated values of the number of ε-caprolactone chains, the designed and measured average molecular weights, and the molecular weight distribution (Mw / Mn) for each reaction. Show.

[0082]

[Table 4]

Next, each poly-ε-caprolactone diol and an equimolar polyisocyanate (MDI) were mixed with 1
The mixture was reacted at 00 ° C. for 5 hours to obtain various kneaded polyurethanes.

To determine the properties of these kneaded polyurethanes as amorphous polymer chains, the glass transition point Tg of each kneaded polyurethane and the stability in low-temperature storage were investigated. Stability at low temperature storage is -15
Judgment was made from the flexibility at 5, 5 and 25 ° C.
Table 5 shows the results.

[0085]

[Table 5]

Further, using each kneading type polyurethane,
Various crosslinked polyurethanes were obtained in the same manner as in Production Example 1. Also,
A physical property test was similarly performed for each crosslinked polyurethane.
Table 6 shows the results.

From the change in the hardness of the crosslinked polyurethane, the molecular weight distribution of the raw material poly-ε-caprolactone diol has a large effect on the increase in hardness (cold hardening) due to the low-temperature crystallization of the elastomer, and the polyol having an extremely narrow molecular weight distribution. It was found that kneading-type elastomers having adjusted low-temperature crystallinity can be provided by using.
In the present invention, the maximum effect can be obtained by using a polyol having a molecular weight distribution of 1.5 or less, preferably 1.3 or less, which is close to monodispersion, which shows a distribution of caprolactone chains. That is, since the average number of chains can be further increased under the condition that the crystallinity is controlled, it becomes possible to obtain a practical glass transition point as a rubber-like elastic body, and a high glass transition point which was conventionally considered to be incompatible can be obtained. It becomes possible to produce an amorphous elastomer composed of a crystalline unit using a general-purpose rubber facility. The practical glass transition point for the rubber-like elastic material here is
For example, it can be defined as −20 ° C. If the glass transition point is -20 ° C or higher, rubber elasticity at room temperature cannot be maintained in a low-temperature environment (0 ° C) that can occur normally.

[0088]

[Table 6]

(Survey for Selection of Initiator Type) In this example, ε-caprolactone was selected as a monomer,
Since ring opening is performed by reacting the ε-caprolactone with the polymerization initiator, the type of the initiator greatly affects the crystallinity of the amorphous polymer chain. Therefore, as shown in Table 7,
As the polymerization initiator, 1,4-butanediol (1,4-
BD), 1,5-pentanediol (1,5-PD),
1,6-hexanediol (1,6-HD), nonanediol (ND), neopentyl glycol (NPG),
3-methyl-1,5-pentanediol (3MPG),
Cyclohexanedimethanol (CHDM), para-xylene glycol (PXG), 1,4-bis (hydroxyethoxy) benzene (BHEB), and BPE-20
(Manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: bisphenol A with ethylene oxide added to both ends by 1 mol)
Was reacted with ε-caprolactone under predetermined conditions to produce various poly-ε-caprolactone diols of Examples 11 to 53. In addition, all the reactions were carried out under a nitrogen stream, and the solution was aged until the residual caprolactone monomer became 1% or less by gas chromatography.

Table 7 shows the amount of catalyst used and the reaction temperature, the designed and calculated values of the number of ε-caprolactone chains, the designed and measured average molecular weights, and the molecular weight distribution (Mw / Mn) for each reaction. Show.

[0091]

[Table 7] In Table 7, MBTO is monobutyltin oxide,
TBT is tetrabutyl titanate.

Each of these poly-ε-caprolactone diols was reacted with an equimolar amount of 4,4′-diphenylmethane diisocyanate (MDI) at 100 ° C. for 5 hours to obtain various kneaded polyurethanes.

In order to determine the characteristics of these kneaded polyurethanes as amorphous polymer chains, the glass transition point Tg and relative crystallinity of each kneaded polyurethane were measured. Here, relative crystallinity refers to the amount of heat of fusion after holding at -10 ° C for 10 hours using a differential scanning calorimeter (DS).
C), which was expressed as weak (weak), medium (medium), and strong (strong) as compared with natural rubber. Table 8 shows the results. In addition, the measurement and analysis of DSC were performed with the following equipment.

[Measurement] Differential Scanning Calorimeter DSC620
0: Seiko Denshi Kogyo Co., Ltd. [Analysis] Thermal analysis, rheology system EXSTAR6
000: manufactured by Seiko Electronic Industry Co., Ltd.

[0095]

[Table 8]

The samples 24, 27,
As described above, various crosslinked polyurethanes were obtained using the kneaded polyurethanes of 32, 37, 39, 42, 47, 51, 56, 60, and 64. In addition, hardness (Hs: JIS A scale), JIS K6255, and the like of various crosslinked elastomers according to JIS K6253.
(Based on ISO4662), the rebound resilience (Rb:
%), Tensile strength (Tb: MPa) and elongation (Eb: JIS K6251 (based on ISO 37)).
%) And the tear strength (Tr: N / mm) according to JIS K6252 (based on ISO34). The initial hardness was measured after a heat treatment at 60 ° C. for 30 minutes and a standing at 23 ° C. for 3 hours. Table 9 shows the results.

[0097]

[Table 9]

As a result, it was found that crystallinity can be finely controlled by setting simple parameters such as the type of initiator and the average number of chains.

The crystallinity of the crosslinked elastomer can be adjusted to some extent by the crosslinked structure and additives, but at least for use at room temperature (20 ° C.), the relative crystallinity is at a high level by crystallization. Failures may occur and are difficult to use. Therefore, in a system using an aliphatic diol as an initiator, the average chain needs to be 6 or less. In other words, if the average chain is 7 or more, crystallization occurs even at room temperature, making it difficult to use as an amorphous polymer chain in an elastomer. When the initiator has a side chain of a methyl group, crystallinity is reduced, but strength is also significantly reduced. On the other hand, when a planar bulky substituent such as a benzene ring or a cyclohexane ring is introduced instead of a methyl group, the crystallinity is moderately moderated, and at the same time, an oriented crystallinity is exhibited at the time of extension to obtain a high-strength elastomer. When a cyclic structure is introduced as described above, the crystallinity is reduced, and the average number of lactone chains can be used up to about 8. However, since the glass transition point is also increased by the introduction of the cyclic structure, the average number of chains is desirably 4 or more in order to keep Tg at -20 ° C or less.

The degree of crystallinity of such an amorphous polymer depends on the number of caprolactone chains, the molecular weight distribution of the caprolactone repeating unit, and the R value of the initiator.
Fine adjustment is possible depending on the kind of _{1 and} the like.For example, although it is amorphous when not stretched, it can easily prepare an amorphous polymer chain that shows oriented crystallinity and good physical properties when stretched. . This is further clarified by the following test.

(Comparison Test on Crystallinity) Samples 4 and 5 of Group A having a narrow molecular weight distribution and Samples 11 and 12 of a group having a wide molecular weight distribution were compared in terms of crystallinity as follows. 1. As measured by a differential scanning calorimeter (DSC),
Measurement of Crystallinity of Amorphous Polymer Chain Before Crosslinking FIG. 2 to FIG. 5 show the results of DSC measurement of the melting behavior of each sample after holding at −10 ° C. for a predetermined time. FIG. 6 shows the measurement results of natural rubber (NR) for comparison.

Sample 1 of Group B having a wide molecular weight distribution
In 1 and 12, it is observed that crystallization is faster than in Samples 4 and 5 of Group A having a narrow molecular weight distribution. It is also recognized that crystallization of caprolactone having an average chain number of 5 is slower than that of 6 having caprolactone. From this, it became clear that fine adjustment of crystallinity can be achieved by setting the average number of chains by using an oligomer having a reduced molecular weight. 2. Comparison of Crystallinity of Crosslinked Elastomer Based on Wide Angle X-Ray Diffraction (WAXD) Measurement Results FIG. 7 to FIG. 10 show WAXD measurement results of each sample. The sample was a sheet processed into a thickness of 1 mm and a width of 3 mm, and measured while varying the elongation. The measurement temperature is 22 ° C. In addition, WA
XD measurement was performed by Liger Flex (Rigaku Denki Co., Ltd.)
At an output of 40 kV and 27.5 mA.

Sample 1 of group B having a wide molecular weight distribution
In Nos. 1 and 12, a diffraction peak due to crystallization is observed even in the non-extended state. Since the peak at 2θ of about 21 ° observed here coincides with the peak position of poly-ε-caprolactone, it is presumed that the extension crystallization of the crosslinked elastomer is caused by crystals of the caprolactone chain.

On the other hand, Samples 4 and 5 of Group A having a narrow molecular weight distribution show an amorphous state in the unstretched and low-stretched regions, and it is presumed that they can be a rubber-like elastic material from the low glass transition temperature. When the elongation is further increased, crystallization is observed. This indicates that, while being a rubber-like elastic body in a deformed state usually used as an elastomer, oriented crystallization occurs in an excessively deformed state due to wear, breakage and the like. In addition, the degree of crystallinity can be finely adjusted by the average chain of caprolactone.

[0105]

As described above, the method for preparing an amorphous polymer chain of the present invention is completely different from the conventional preparation method and controls the number of chains of monomer units of the crystalline oligomer and the molecular weight distribution of the chain units. By doing so, it is possible to prepare an amorphous polymer chain using a crystalline oligomer which was conventionally considered to be too strong and unusable, thereby improving the degree of freedom in industrial preparation. This has the effect that it can be performed.

[Brief description of the drawings]

FIG. 1 is a diagram showing the temperature dependence of rebound resilience.

FIG. 2 is a view showing a DSC measurement result of Sample 4.

FIG. 3 is a view showing a DSC measurement result of Sample 11.

FIG. 4 is a view showing a DSC measurement result of Sample 5.

FIG. 5 is a view showing a DSC measurement result of Sample 12.

FIG. 6 is a diagram showing the measurement results of DSC of natural rubber.

FIG. 7 is a view showing a measurement result of WAXD of Sample 4.

FIG. 8 is a diagram showing a measurement result of WAXD of Sample 11.

FIG. 9 is a view showing a measurement result of WAXD of Sample 5.

FIG. 10 is a view showing a measurement result of WAXD of Sample 12.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C08G 85/00

Claims (16)

(57) [Claims] 1. A system comprising a predetermined number of monomer units.
And having a repeating unit having a predetermined molecular weight distribution
Selecting a crystalline oligomer,
A compound that reacts with the end of ligoma.
Select a binding unit that inhibits the crystallinity of the oligomer.
And a combination unit that inhibits the crystallinity of the oligomer by combining these steps.
The oligomer is alternately linked, and the oligomer is in an elastic state in which the crystallinity of the oligomer is restricted under normal use conditions and exhibits rubber elasticity, and an oriented crystallization state in which the crystallinity is developed by excessive deformation. A method for preparing an amorphous polymer chain in an elastomer, wherein the polymer chain is reversibly possessed. 2. The method for preparing an amorphous polymer chain in an elastomer according to claim 1 , wherein the linking is by polyaddition or polycondensation. 3. The method for preparing an amorphous polymer chain in an elastomer according to claim 1, wherein the glass transition temperature of the amorphous polymer chain is −20 ° C. or less. 4. The method according to claim 1 , wherein
While the crystalline oligomer is a crystalline polyol having hydroxyl groups at both ends, the compound that reacts with the crystalline oligomer is a diisocyanate, and the binding unit is a urethane binding unit derived from diisocyanate. A method for preparing an amorphous polymer chain in an elastomer. In any one of claims 5] claims 1-4, said crystalline oligomer having repeating units composed of a chain of monomer units derived from the cyclic monomers by ring-opening adding a cyclic monomer to the initiator A method for preparing an amorphous polymer chain in an elastomer, wherein the method comprises forming and forming a part of the binding unit with the initiator. 6. The method according to claim 5 , wherein the repeating unit of the chain of monomer units is ε-caprolactone.
The crystalline oligomer is represented by the following formula, the average value of the caprolactone chain in the poly-ε-caprolactone diol is a predetermined number, and the poly-ε
-A method for preparing an amorphous polymer chain in an elastomer, wherein a molecular weight distribution Mw / Mn of a caprolactone diol portion of a caprolactone diol is set to 1.0 to 1.5. Embedded image (Here, [] indicates a caprolactone chain portion, and m
And n indicate the number of chains, and R ₁ is a polymerization initiator R ₁ (O
H) derived from ₂ ) 7. The molecular weight distribution Mw according to claim 6 , wherein
A method for preparing an amorphous polymer chain in an elastomer, wherein / Mn is from 1.0 to 1.3. 8. The method according to claim 6 , wherein the poly-
ε-caprolactone diol polymerization initiator R ₁ (O
H) ₂ is a linear glycol having 2 to 12 carbon atoms; diols having a side chain having 12 or less carbon atoms such as neopentyl glycol and 3-methyl-1,5-pentanediol;
And at least one selected from the group consisting of diols having an unsaturated group having 12 or less carbon atoms, such as 3-allyloxy-1,2-propanediol, wherein the average value of the caprolactone chain is in the range of 3 to 6. A method for producing an amorphous polymer chain in an elastomer. 9. The poly-ε-caprolactone diol polymerization initiator R ₁ (OH) _{2 according} to claim 8 , wherein the poly (ε-caprolactone) diol polymerization initiator R ₁ (OH) ₂ is a linear glycol having 2 to 12 carbon atoms and does not contain a side chain such as a methyl group. A method for producing an amorphous polymer chain in an elastomer, wherein the method is at least one selected from the group consisting of: 10. The polymerization initiator R ₁ (O ) according to claim 6 or 7 , wherein the polymerization initiator of the poly-ε-caprolactone diol is used.
H) ₂ is at least selected from the group consisting of diols containing an aromatic ring such as 1,4-bis (hydroxyethoxy) benzene and para-xylene glycol; and alicyclic diols such as cyclohexanediol and cyclohexanedimethanol. A method for producing an amorphous polymer chain in an elastomer, wherein the average value of the caprolactone chain is 4 to 8. 11. The amorphous polymer according to claim 5 , wherein the polyol contains a chain extender in addition to the long-chain diol containing the poly-ε-caprolactone diol. How to prepare molecular chains. 12. In any one of claims 4 to 11, moth
A method for preparing an amorphous polymer chain in an elastomer, wherein a lath transition temperature Tg is −20 ° C. or less. 13. The diisocyanate according to claim 4 , wherein the diisocyanate is 2,6-toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate (PPDI), 1,5 -Naphthalene diisocyanate (NDI) and 3,3-dimethyldiphenyl-4,4 '
-A method for preparing an amorphous polymer chain in an elastomer, which is at least one selected from diisocyanates (TODI). 14. An elastomer according to claim 4 , wherein said poly-ε-caprolactone diol is produced under a reaction condition of 130 ° C. or lower using a tin catalyst represented by the following formula. For preparing an amorphous polymer chain in the above. Embedded image (Where R ₂ represents hydrogen, an alkyl group or an aryl group, X represents a hydroxyl group, an alkoxide group or a halogen other than fluorine) 15. In any one of claims 1 to 3, wherein
While the crystalline oligomer with a diol, the crystallinity cage
An amorphous polymer in an elastomer characterized by using a compound that reacts with sesame as a diisocyanate, designing a cast or thermoplastic polyurethane soft segment, and preparing the cast or thermoplastic polyurethane with the soft segment and the hard segment. How to prepare the chains. 16. The method according to claim 1 , wherein
A method for preparing an amorphous polymer chain in an elastomer, wherein a crystalline oligomer is a dicarboxylic acid, while a compound reacting with the oligomer is a diamine, and the bonding unit is an amide bond.