JPH0778115B2 - Method for producing crosslinked polymer molding and combination of reactive solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application In the present invention, a metathesis-polymerizable monomer is poured into a mold in the presence of a metathesis polymerization catalyst system, and then bulk-polymerized to perform molding simultaneously with polymerization. The present invention relates to a method for producing a polymer molded article having improved impact resistance. More specifically, in the above metathesis polymerization, by copolymerizing a metathesis polymerizable monomer having a long side chain, internal plasticization, to improve the impact resistance of the resulting crosslinked polymer molded product. It is about.

b. Prior Art It is known that cyclic olefins are cleaved by metathesis polymerization catalysts to give polymers. Therefore, a method in which a monomer having two metathesis-polymerizable groups, such as dicyclopentadiene, that is obtained at low cost is poured into a mold in a liquid state and bulk polymerization is performed therein to obtain polymerization and molding in one step. Has been proposed (see, for example, JP-A-58-129013).

Such a method can be used in a wide range of applications because a large-sized molded product can be obtained using an inexpensive mold. However, there are many applications in which such a large-sized molded article is required to have good impact resistance. However, in general, when a metathesis-polymerizable monomer as described above, particularly a crosslinkable monomer, is used, the resulting molded product often lacks impact resistance. As a method for improving it, a method of forming a polymer molded product by allowing a soluble rubber to coexist in a monomer,
A method of adding a plasticizer has been proposed. The method of adding a plasticizer generally has a problem of blooming of the added plasticizer, and it cannot be said to be a satisfactory method. On the other hand, the method of adding rubber can be said to be an effective method because a considerably large effect is recognized even if a small amount is added. However, the addition of such a rubber greatly increases the viscosity of the reactive solution of the monomer. On the other hand, it is necessary to have a low viscosity in order to efficiently pour the reactive solution of the monomer into the template while mixing it. In such a method, even in the reaction injection molding method using high-pressure collision mixing capable of handling the most viscous monomer liquid, generally only those having a viscosity of several poises are treated, and glass fiber or the like is impregnated with a monomer premix and solidified. It was found that methods such as resin transfer molding are required to have a lower viscosity, and the amount in which the rubber component can be dissolved is extremely limited. That is, it has been found that the method of adding a general rubber has a problem that the addition amount is limited due to the viscosity of the monomer liquid, and the application cannot be sufficiently dealt with for applications requiring higher impact resistance.

Therefore, the present inventor has arrived at the present invention as a result of earnest research on a method for obtaining a polymer molded product by metathesis polymerization, which has a higher impact resistance and a good elastic property.

C. Structure of the invention That is, the present inventors, like the plasticizer, if the metathesis polymerizable monomer having a side chain of a certain degree or more long chain is selected, if the polymer is internally plasticized by copolymerization It has been found that a polymer molded product can be obtained which does not have a problem as in the case of using an ordinary plasticizer such as blooming.

The present invention has been achieved based on such findings and includes the following inventions.

(1) In a method of bulk-polymerizing a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molded product, at least one metathesis polymerizable group in a molecule and inhibition of rotation are used as raw material monomers. At least 1 monovalent chain organic group having 5 or more atoms
3-50 in the metathesis-polymerizable monomer
A method for producing an internally plasticized crosslinked polymer molded article, which comprises using a raw material monomer containing mol% and performing polymerization and molding simultaneously.

(2) a) Reactive solution of metathesis polymerizable monomer containing catalyst component of metathesis polymerization catalyst system (solution A) b) Reactive solution of metathesis polymerizable monomer containing activator component of metathesis polymerization catalyst system (solution B) In a combination of at least reactive solutions consisting of at least one of the solutions A and B, the metathesis-polymerizable monomers of the solutions A and B have a composition in which both solutions have at least one metathesis-polymerizable group in the molecule and 5 atoms that are not hindered by rotation. Of a monomer having at least one monovalent linear organic group having 3 or more of them is a raw material monomer containing 3 to 50 mol% of the metathesis-polymerizable monomer. Combination of reactive solutions for.

The side chain-containing metathesis polymerizable monomer used in the present invention, as a side chain having flexibility, a cyclic structure, SP ₂ bonds, etc., except for the portion where the flexibility of the chain portion is inhibited, inhibits rotation. It is necessary that they have at least 5 unrepaired atoms, which are also preferably continuous. Such a side chain does not necessarily have to consist of a hydrocarbon chain, and may contain oxygen or the like. Needless to say, it does not have to be a straight chain, and it is often the case that an appropriate amount of branching is contained so that the plastic action can be more efficiently exhibited. However, if the chain length is too long, it may be difficult to purify the monomer by distillation or the like, and 16 or less is generally used.

Further, as the metathesis-polymerizable group, a group having a norbornene structure in general, particularly a norbornene group itself, is suitable.

Further, the metathesis-polymerizable monomer is not limited to hydrocarbon, and may be a substance containing a different element such as oxygen, nitrogen, or halogen.

That is, it does not matter if it contains an aprotic polar group such as ester, ether or N-substituted imine. The polar group having an action as such a Lewis base has an action of retarding the initiation of metathesis polymerization, and by positively utilizing such action, the resin is transferred to a mold after the premixed state as described above. It can be applied to the transfer method. In such a method, a monomer liquid having a lower viscosity is required, it becomes very difficult to add rubber as described above, and the method of the present invention can be suitably used. Therefore, both polar group-containing monomers are used. You will be able to use the function of.

Further, in the production of the side chain-containing monomer of the present invention, it is often industrially and easily produced by utilizing an intermediate having a polar group.

Specific examples of the side chain-containing monomer having such a suitable polar group are as follows.

(2-Ethylhexyl) norbornene-5-carboxylate (2-Ethylhexyl) 5-methylnorbornene-5-
Carboxylate Nadic acid dibutyl ester Butyl norbornene-5-carboxylate Preferable examples thereof include higher alkyl esters such as nadic acid and 5-norbornenecarboxylic acid. Higher alkyl esters of acrylic acid, methacrylic acid, maleic acid and fumaric acid, which are the precursors of these, are industrially produced for use as internal plasticizers of various resins, and they can be used advantageously.

Also, (5-norbornenyl) methyl- (isobutyl) ether (5-norbornenyl) methyl- (2-ethylhexyl) -ether (5-norbornenyl) methyl-nonylphenyl ether Ether-containing monomers such as; N-nonyl nadic imide N-hexyl nadic imide And N-substituted imide group-containing monomers such as; and polar group-containing monomers such as.

5-heptyl norbornene as a hydrocarbon monomer 5-dodecylbenzene norbornene And so on.

On the other hand, as the other metathesis polymerizable monomer used together with the side chain-containing metathesis polymerizable monomer, any one may be used as long as it gives a rigid molded product by bulk polymerization by the metathesis polymerization catalyst system as a monomer liquid, 1 to 4 metathesis-polymerizable cycloalkene groups
The one containing one is used. Those having a norbornene-type bond are particularly preferable. Hydrocarbons are particularly preferable, and specific examples thereof include dicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, 5-vinyl norbornene, 5-cyclohexenyl norbornene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,
6,7,8,8a-octahydronaphthalene, 6-ethylidene-
1,4,5,8-Dimethano-1,4,4a, 5,7,8,8a-heptahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a- Hexahydronaphthalene, tricyclo [8,2,1,0] trideca
Examples thereof include 5,11-diene, norbornadiene, 5-phenylnorbornene and ethylenebis (5-norbornene). Especially, dicyclopentadiene is particularly preferable.

Further, if necessary, a metathesis-polymerizable monomer having a different element such as oxygen or nitrogen can be used. The metathesis-polymerizable monomer also preferably has a norbornene structural unit, and the polar group is preferably an ester group, an ether group, a cyano group, an N-substituted imide group, or the like.

Such a polar group, as a Lewis base, has the effect of controlling the initiation rate of the metathesis polymerization reaction, and also has the effect of introducing a polar group into the formed polymer molded product. It is preferably used when action is required. Examples of such polar monomers include (5-norbornenyl) methyl-phenyl ether, bis [(5-norbornenyl) methyl] ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, ethylene-bis (5- Norbornenecarboxylate), 5-cyanonorbornene, 6-cyano-
1,4,5,8-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, N-butyl nadic acid imide, 5- (4
-Pyridyl) -norbornene and the like can be mentioned.

Further, a halogen-containing / metathesis polymerizable monomer can be used for improving flame retardancy and softening temperature. Specific examples of such a monomer include 5-chloronorbornene, 5-bromonorbornene, 5,5,6-trichloronorbornene, 5,
Examples thereof include 5,6,6-tetrachloronorbornene and 5,6-dibromonorbornene 5- (2,4-dibromophenyl) norbornene.

It is preferable that the metathesis-polymerizable monomers as described above all have the content of impurities that inhibit the metathesis polymerization catalyst as small as possible.

The side chain-containing metathesis-polymerizable monomer used in the present invention is generally used in the range of 3 to 50 mol% in all monomers. The more preferable range depends on the kinds of the side chain-containing metathesis polymerizable monomer and the main structure metathesis polymerizable monomer used, and the performance of the molded product, and it is necessary to experimentally determine the optimum use ratio accordingly. A generally preferred range is from 5 to 40 mol%.

In the present invention, the metathesis polymerization catalyst system used to obtain polymer moldings is generally formed from two components, a catalyst component and an activating component.

Such a metathesis polymerization reaction is an exothermic reaction, and once the polymerization is started, the system is further heated to accelerate the reaction.

Therefore, as described above, two solutions, that is, a solution mainly composed of a monomer and a catalyst component (solution A) and a solution mainly composed of a monomer and an activator component (solution B) are prepared in advance and subjected to collision mixing or static mixer. A method is used in which rapid mixing is performed by, for example, pouring into a mold immediately, shaping, and then curing in the mold. In this case, the composition of the monomer does not necessarily have to be both liquids, and can be appropriately changed depending on the function of the monomer.

For example, when the above polar monomer is copolymerized to use the function as a polymerization initiation regulator, a large amount can be added to the solution (B). Also, the side chain-containing metathesis polymerizable monomer should be added only to either the solution (A) or the solution (B) when there is a concern that the interaction with the main catalyst component or the activator will occur. Is also possible.

As another method for obtaining a polymer molded product, a Lewis base acting as a regulator for delaying the initiation of metathesis polymerization or a metathesis polymerization monomer having such a Lewis base is added as described above to delay the initiation of polymerization and to generate it in advance. A method of injecting the premix into the mold, that is, a method of resin injection can be used. In this case, it is advantageous to obtain a fiber reinforced molded product by placing a glass fiber mat or the like in advance in the mold.

In particular, as described above, the side chain-containing metathesis polymerizable monomer of the present invention is suitable for the premix method requiring a low viscosity monomer liquid, as described above.

Salts such as halides of tungsten, rhenium, tantalum, molybdenum and the like are used as a catalyst component in the metathesis polymerization catalyst system, but a tungsten compound is particularly preferable. As such a tungsten compound, tungsten halide, tungsten oxyhalide and the like are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride and the like are preferable. Further, organic ammonium tungstate or the like can also be used. It has been found that such a tungsten compound immediately starts cationic polymerization when added directly to the monomer, which is not preferable. Therefore, the tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene or the like in advance and solubilized by adding a small amount of an alcohol compound or a phenol compound before use.

Further, as described above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile. When a polar monomer is used, it may be a Lewis base as described above, and it may have the action even without adding the above-mentioned compound.

Thus, the monomer solution containing the catalyst component (solution A) is
It has practically sufficient stability.

On the other hand, the activator component in the metathesis polymerization catalyst system is preferably an organometallic compound centered on an alkylated compound of a metal of Groups I to III of the Periodic Table, particularly an alkyltin, an alkylaluminum compound, an alkylaluminum halide compound, and Include diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum,
Dioctyl aluminum iodide, tetrabutyl tin, etc. can be mentioned. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the activator component in the raw material monomer.

In the present invention, basically, a crosslinked polymer molded product can be obtained by mixing the solution A and the solution B, but with the above composition as it is, the polymerization reaction is started very quickly, Since curing often occurs before it sufficiently flows into the casting mold, this often causes a problem, and as described above, it is preferable to use an activity modifier for that purpose.

As such a regulator, Lewis bases are generally used, and ethers, esters, nitriles and the like are used. Specific examples thereof include ethyl benzoate, butyl ether, diglyme, and the like. Such a regulator is generally used by adding it to the solution side of the component of the activator of the organometallic compound. When a monomer having a Lewis base group is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the raw material monomer is about 10 on a molar basis.
When the activator component is an alkylaluminum, the ratio of the aluminum compound to the raw material monomer is about 100 on a molar basis. Around 1 to about 2000 to 1, preferably about 200 to 1 to about 500 to 1 is used. Further, as described above, the masking agent and the regulator can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The crosslinked polymer molded product according to the present invention may further contain various additives in order to improve or maintain its properties in practical use. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers and the like. Such additives cannot be added after the crosslinked polymer of the present invention has been molded, and therefore, when added, it is necessary to add them to the above raw material solution in advance.

The easiest method is the solution A and the solution B.
One or both of them can be added in advance.In that case, the catalyst component having a strong reactivity in the liquid or the activator component does not react to some extent in practice, and the polymerization Must not interfere with In any case, if the reaction is unavoidable but coexistence does not substantially inhibit the polymerization, it is possible to mix with the monomer to prepare the third liquid, and to use the mixture immediately before the polymerization. . Further, in the case of a solid filler, both components are mixed, and immediately before starting the polymerization reaction or while polymerizing, those having a shape capable of sufficiently filling the voids, in the molding mold, It is also possible to fill it.

The reinforcing material or filler as an additive is effective in improving the bending modulus. Examples of such materials include glass fiber, mica, carbon black, wollastonite and the like. Those obtained by surface-treating these with a so-called silane coupler can also be suitably used.

In addition, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-
Di-t-butyl-p-cresol, N, N'-diphenyl-
p-phenylenediamine, tetrakis [methylene (3,5
-Di-t-butyl-4-hydroxycinnamate)] methane and the like.

The crosslinked polymer molded product of the present invention is characterized in that it is internally plasticized by copolymerizing a side chain-containing metathesis polymerizable monomer to improve impact resistance. As described above, by utilizing the plasticization by copolymerization, it is possible to obtain a molded product having a wider impact resistance than that in the case where the solid rubber is added. A lower molecular weight liquid rubber is also used in a small amount, generally 5% by weight or less, more usually 3 as long as the characteristics of the present invention are not impaired.
Weight% or less can be used together. Examples of the elastomer used for such purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-dienta-polymer, nitrile rubber and the like.

The crosslinked polymer molded product of the present invention is produced by simultaneously performing polymerization and molding as described above.

As the molding method, as described above, the resin injection method in which the catalyst system and the monomer mixture are mixed in advance into the mold, the solution A and the solution B in which the catalyst system is divided into two are collided at the head portion. It is possible to adopt the RIM method in which it is mixed and poured into the mold as it is. In either case, the injection pressure into the mold can be relatively low, and thus inexpensive molds can be used.

Further, when the polymerization reaction in the mold starts, the temperature in the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike the case of polyurethane-RIM, it is easy to release from the mold, and a special release agent is often unnecessary.

Since the molded product has an oxide layer on the surface, it has good adhesion to commonly used paints such as epoxy and polyurethane.

d. Effect of the Invention The molded product thus obtained has impact resistance, that is, flexibility, improved by internal plasticization as compared with the conventional one,
It can be used for a wide range of applications, centering on large moldings such as parts of various transportation equipment including automobiles, housings of electric and electronic equipment.

e. Examples Hereinafter, the present invention will be described in detail with reference to Examples. It should be noted that the embodiment is for the purpose of explanation and is not limited thereto.

Examples 1 to 26, Comparative Example [Preparation of Raw Material Monomer] Commercially available DCP was purified by distillation in a nitrogen stream under reduced pressure to give a freezing point of 3
Purified dicyclopentadiene showing 3.4 ° C. was obtained. Purity measurement by gas chromatography showed a purity of 99% or higher.

On the other hand, commercially available dicyclopentadiene is thermally dissociated to obtain cyclopentadiene, and 5-butoxycarbonylnorbornene (BC
N) was synthesized. Further, nadic acid dibutyl ester (NDB) was synthesized by a method of reacting maleic acid dibutyl ester, and 5-methyl-5 (2-ethylhexyl) carbonylnorbornene (MEHCN) was synthesized by a method of reacting 2-ethylhexyl methacrylate.
Further, by reacting 2-ethylhexyl acrylate, 5 (2-ethylhexyl) carbonylnorbornene (EHCN) was converted to di (2-ethylhexyl) maleate.
Was reacted to synthesize nadic acid di (2-ethylhexyl) ester (NBEH).

These compounds were analyzed by gas chromatograph for purity.
It was over 99%.

[Preparation of Catalyst Component Solution] 20 g of tungsten hexachloride was added to 70 ml of dry toluene under a nitrogen stream, and then a solution of 21 g of nonylphenol and 16 ml of toluene was added to prepare a 0.5 M tungsten-containing catalyst solution. On the other hand, nitrogen gas was purged overnight to remove hydrogen chloride gas generated by the reaction between tungsten hexachloride and nonylphenol, to obtain a polymerization catalyst.

10 ml of such solution, 1.0 ml of acetylacetone monomer mixture 50
0 ml was mixed to prepare a solution A having a tungsten content of 0.01M.

[Preparation of activator component solution] Trioctylaluminum 85 was prepared at a molar ratio of dioctylaluminum iodide 15 and diglyme 300, and 500 ml of a mixed monomer was mixed to prepare 0.03M solution B as an aluminum content. did.

The molar ratio of the carboxylic acid ester and the copolymerization component in the monomer mixture in the solution is shown in the following table.

10 ml of the catalyst component solution (Solution A) and 10 ml of the activator component solution (Solution B) were heated to a predetermined temperature, and the solution was sufficiently replaced with nitrogen and taken out into a syringe. Both liquids are simultaneously extruded from the syringe at a constant speed into a glass flask with a stirrer under rapid agitation, and after rapid mixing, a stirrer is raised and a thermocouple is pushed in. The time reached (polymerization time) was measured.

Further, the solidified cross-linked resin was taken out and cut into pieces to measure the softening point in a nitrogen stream in the TMA method-needle penetration mode.
The swelling rate was measured with another sample. The results are summarized in Table 2.

Further, each of the liquids A and B of each example was taken out into 10 ml of silidine, and it was mechanically introduced at a constant speed into an extrusion nozzle,
Then, when it was molded with an ultra-small RIM machine that can be collision-mixed and poured into the mold, a brown tough plate with a thickness of 3 mm could be molded. The Izod strength with a notch was measured using this pad and is also shown in the table.

From the mixing temperature and the polymerization time, the reaction initiation temperature tends to increase and the reaction time tends to increase as the addition amount of these compounds increases, which is advantageous for obtaining a relatively large crosslinked polymer molded product. Becomes And the obtained resin is a flexible and tough molded product with a low softening point, and it is clear from the measurement results of the impact resistance of the notched Izod that it is greatly improved compared to the comparative example. .

Examples 27 to 30 Butyl nadic acid imide (BNI) was synthesized by a dehydration reaction of nadic anhydride and butyl amine in acetonitrile by heating under reflux in toluene. The reaction mixture was distilled and purified under reduced pressure. And nadic anhydride 2
2-Ethylhexyl nadic acid imide (BHNI) was synthesized by a similar reaction with -ethylhexylamine.

The purity of these compounds was 99% or more in the purity analysis by gas chromatography.

The structure was confirmed by MS, IR and NMR. The polymerization was carried out in the same manner as in Example 1 except that the mixture was mixed with the monomers in the molar ratios shown in Table 3. The results are shown in Table 4.

From the mixing temperature and the polymerization time, the reaction initiation temperature tends to increase and the reaction time tends to increase as the addition amount of these compounds increases, which is advantageous for obtaining a relatively large crosslinked polymer molded product. Becomes In addition, the obtained resin was a flexible and tough crosslinked polymer molding, and it was found from the measurement results of the impact resistance of the notched Izod that the resin was significantly improved as compared with the comparative example.

Example 31 Butyl (5-norbornenylmethyl) ether (BNE) was synthesized by a method in which cyclopentadiene obtained by thermally dissociating commercially available dicyclopentadiene and allyl butyl ether were reacted in an autoclave. This compound is 0.2mmHg
It was obtained from a 44 ° C distillate under reduced pressure, and was 99% or more in purity analysis by gas chromatography. The structure is M
Confirmed by S, NMR and IR.

The copolymerization with DCP was carried out in the same manner as in Example 1 using a mixture of 90 mol% DCP and 10 mol% BNE, the polymerization initiation temperature was 50 ° C, the temperature reached above 100 ° C in 7 seconds, and the maximum temperature reached was 187 ° C. Compared with the comparative example, the temperature at the time of mixing becomes higher and the polymerization time becomes longer. Therefore, the addition of BNE is advantageous in obtaining a molded product larger than the comparative example. The softening point measured by TMA was 78 ° C, and the impact resistance measured by the notched Izod was 46 kg · cm / cm. From this, it is understood that the resin obtained is flexible with a low softening point and excellent in impact resistance.

Example 32 5-Hexylnorbornene (HNB) was synthesized by a method of reacting commercially available dicyclopentadiene and 1-octene at 170 ° C. in an autoclave. This compound is 0.7mm
It was obtained from a fraction at 60 ° C. under reduced pressure of Hg, and the purity was 99% or more in a purity analysis by gas chromatography. The structure was confirmed by NMR and MS.

The copolymerization with DCP was carried out in the same manner as in Example 1 with a mixture of DCP 80 mol% and HNB 20 mol%, and the polymerization initiation temperature was 35 ° C., and after mixing, the temperature reached 100 ° C. in 32 seconds, and the maximum temperature reached was 173 ° C. TMA
The softening point was measured by 83 ° C., and the impact resistance measured by the notched Izod was 7.5 kg · cm / cm. This shows that the impact resistance is improved as compared with the comparative example.

Claims (2)

[Claims] 1. A method for bulk-polymerizing a metathesis polymerizable monomer in the presence of a metathesis polymerization catalyst system to obtain a crosslinked polymer molded product, comprising at least one metathesis polymerizable group in a molecule as a raw material monomer, and rotation. Of a monomer having at least one monovalent chain organic group having 5 or more atoms that do not inhibit
A method for producing an internally plasticized crosslinked polymer molded article, which comprises using a raw material monomer in an amount of ˜50 mol% and performing polymerization and molding simultaneously. 2. A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A). B) A reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system. In a combination of at least reactive solutions consisting of solution B), the metathesis-polymerizable monomers of solution A and solution B are such that the combined composition of both solutions has at least one metathesis-polymerizable group in the molecule and an atom that does not inhibit rotation. A crosslinked polymer molded article, which is a raw material monomer containing 3 to 50 mol% of a monomer having at least one monovalent chain organic group having 5 or more Of reactive solutions for the manufacture of.