CN114276491A - Liquid ruthenium carbene catalyst composition and application thereof in preparation of cyclic olefin resin - Google Patents
Liquid ruthenium carbene catalyst composition and application thereof in preparation of cyclic olefin resin Download PDFInfo
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Abstract
The invention provides a liquid ruthenium carbene catalyst composition and application thereof in preparation of cycloolefin resin. Specifically, the present invention provides a liquid catalyst composition containing a ruthenium carbene catalyst, which contains a ruthenium carbene catalyst, a solvent and an optional stabilizer, wherein the solvent contains an unsaturated acid anhydride containing a C ═ C structure and having no more than 20 carbon atoms in a molecule and/or an ester containing a C ═ C structure and having no more than 20 carbon atoms in a molecule. The catalytic system is stored at room temperature and has good storage stability. The liquid catalyst composition is matched with a liquid cycloolefin/cycloolefin composition for use, and the continuous automatic production of the thermosetting cycloolefin resin can be realized.
Description
Technical Field
The invention relates to a liquid ruthenium carbene catalyst composition and application thereof in preparation of cyclic olefin resin.
Background
The ruthenium carbene catalyst has good effect on Ring Opening Metathesis Polymerization (ROMP) of a composition containing dicyclopentadiene (DCPD), Tricyclopentadiene (TCPD) and other cyclic olefins by injection Reaction Injection Molding (RIM), Resin Transfer Molding (RTM) and other process methods, and the catalyst has good water resistance and oxygen resistance and low requirements on production equipment. However, the commonly used ruthenium carbene catalyst or the composition of the ruthenium carbene catalyst and the chlorinated paraffin is a solid or highly viscous colloidal substance, and is difficult to be directly used in the process of continuous production. Therefore, the ruthenium carbene catalyst is often dissolved in a certain amount of solvent for use in the prior art. Since such catalysts have poor solubility in cyclic olefins represented by DCPD and compositions thereof and have very strong reactivity when mixed with such substances, aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, etc.), alkanes, cycloalkanes, methylene chloride, tetrahydrofuran, ethyl acetate, and other weakly polar solutions are often used as solvents in practical use. However, in the above-mentioned conventional solvents, the ruthenium carbene catalyst may cause the ligand on the catalyst to fall off, and the storage time is extremely short, and the catalyst solution is usually deactivated within 24 hours after the preparation, and thus it is necessary to use the catalyst solution as it is. Furthermore, the use of the above-mentioned solvents may result in that the "surface flow mark" of the cured product of the cycloolefin composition may be increased and the mechanical properties may be degraded.
CN112547126A discloses an application of ruthenium carbene composition, wherein a formula of dicyclopentadiene/epoxy resin composite material is disclosed: mixing dicyclopentadiene and epoxy resin to form a component A, and mixing the dicyclopentadiene and the epoxy resin to form a component B, wherein the component B comprises a ruthenium carbene catalyst composition, methyl-5-norbornene-2, 3-dicarboxylic anhydride (an epoxy curing agent and a comonomer), a coupling agent KH560 and an anti-aging agent; the formula of another dicyclopentadiene/epoxy resin composite material is also disclosed as follows: mixing dicyclopentadiene and epoxy resin to form a component A, and mixing a ruthenium carbene catalyst-chlorinated paraffin composition, methyltetrahydrophthalic anhydride (epoxy resin curing agent), 2-methylimidazole (curing agent accelerator), glass fiber and a silane coupling agent A172 to form a component B.
CN112662129A discloses a resin composition, a composite material and a preparation method thereof, wherein a formula for preparing polydicyclopentadiene is disclosed: dicyclopentadiene, graphite powder and triphenylphosphine are mixed to be used as a component A, and a catalyst-chlorinated paraffin composition and methyl-5-norbornene-2, 3-dicarboxylic anhydride (comonomer) are mixed to be used as a component B. The methods disclosed in the two applications, when the ruthenium carbene catalyst and the chlorinated paraffin are pre-prepared into a catalyst composition, form a high-viscosity material, which is not beneficial to operation.
Therefore, to realize the application of ruthenium carbene catalysts in the continuous automated production of polycycloolefin resin materials, it is necessary to obtain a low viscosity catalyst solution/dispersion system with storage stability.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a stable low viscosity (≦ 450mPa · s, 25 ℃) liquid catalyst composition formed by dissolving a ruthenium carbene catalyst in an unsaturated acid anhydride having a C ═ C structure and having no more than 20 carbon atoms in the molecule and/or an ester having a C ═ C structure and having no more than 20 carbon atoms in the molecule. The liquid catalyst composition is matched with a liquid cycloolefin/cycloolefin composition for use, so that the continuous automatic production of the thermosetting cycloolefin resin can be realized, and the catalytic system is stored at room temperature, has good storage stability and can overcome the defects in the prior art.
Accordingly, in a first aspect, the present invention provides a liquid catalyst composition comprising a ruthenium carbene catalyst, the liquid catalyst composition comprising a ruthenium carbene catalyst, a solvent and optionally a stabilizer, wherein the solvent comprises an unsaturated acid anhydride having a C ═ C structure and having no more than 20 carbon atoms in a molecule and/or an ester having a C ═ C structure and having no more than 20 carbon atoms in a molecule.
In one or more embodiments, the ruthenium carbene catalyst is a Grubbs first generation catalyst, a Grubbs second generation catalyst, and/or a ruthenium carbene compound according to formula I:
wherein R in the formula I1And R2Each independently is C4-C18 alkyl or substituted with R1-1Substituted C4-C18 alkyl; r1-1Is a C6-C10 aryl group; mes is mesityl; cy is cyclohexyl.
In one or more embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl group of the substituted C4-C18 alkyl groups may independently be a C4-C10 alkyl group.
In one or more embodiments, the group is R1-1In the substituted C4-C18 alkyl group, R1-1The number of (B) is 1,2 or 3, and when 2 or 3, R is1-1The same or different.
In one or more embodiments, the C6-C10 aryl is phenyl or naphthyl.
In one or more embodiments, the R is1And R2The same or different.
In one or more embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl group of the substituted C4-C18 alkyl groups is independently a C4-C6 alkyl group.
In one or more embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl groups in the substituted C4-C18 alkyl groups are each independently C4 alkyl, C5 alkyl, or C6 alkyl.
In one or more embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl groups in the substituted C4-C18 alkyl groups are each independently n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl.
In one or more embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl groups in the substituted C4-C18 alkyl groups are each independently n-butyl or n-hexyl.
In one or more embodiments, R1And R2Each independently is a C4-C18 alkyl group.
In one or more embodiments, the ruthenium carbene compound represented by formula 1 is any one of the following structures:
in one or more embodiments, the unsaturated anhydride is a cyclic anhydride comprising the structure:
wherein the wavy line indicates the position at which the structure is attached to the remainder of the cyclic anhydride; preferably, the rings in the cyclic anhydride are bridged, spiro or fused rings, optionally containing an additional heteroatom in the ring other than the anhydride-forming O, the additional heteroatom being selected from O, S and N, and the ring being optionally substituted with 1-6 substituents selected from halogen and C1-C4 alkyl.
In one or more embodiments, the ester is a mono-or poly-ester, at least one of the fatty acid chains and the fatty alcohol chains forming the ester containing a C ═ C double bond; preferably, at least one of the fatty acid chain and the fatty alcohol chain contains a ring structure; preferably, the ring structure is a bridged, spiro or fused ring; preferably, the ring structure is an unsaturated ring containing the C ═ C double bond.
In one or more embodiments, the ring in the cyclic anhydride is an unsaturated ring containing the C ═ C structure.
In one or more embodiments, the ring structure of the ester includes C4-C8 cycloolefins or C4-C8 bridged cycloolefins, such as bicyclo [2.2.1] -2-heptene and cyclohexene; preferably, the fatty acid chains of the esters are derived from the fatty acid chains of 5-norbornene-2, 3-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid and maleic acid; preferably, the fatty alcohol chain of the ester is a fatty acid chain of a C1-C4 alcohol.
In one or more embodiments, the unsaturated anhydride and/or ester is selected from the group consisting of maleic anhydride, 5, 6-dimethyl-3 a,4,7,7 a-tetrahydro-2-benzofuran-1, 3-dione, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, 1,2,5, 6-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, biphenyl anhydride, exo-nadic anhydride, endo-nadic anhydride, exo-furan-maleic anhydride adduct, exo-cyclohexene-maleic anhydride adduct, 5-norbornene-2, 3-dicarboxylic acid dimethyl ester, and mixtures thereof, One or more of 4-cyclohexene-1, 2-dicarboxylic acid dimethyl ester, 3-cyclohexene-1-carboxylic acid methyl ester and diethyl maleate.
In one or more embodiments, the liquid catalyst composition contains from 0.5 to 50 wt%, preferably from 3 to 40 wt%, more preferably from 5 to 30 wt% of the ruthenium carbene catalyst, based on the total weight of the liquid catalyst composition.
In one or more embodiments, the liquid catalyst composition contains from 35 to 99.5 wt%, preferably from 75 to 95 wt%, of the unsaturated anhydride and/or ester, based on the total weight of the liquid catalyst composition.
In one or more embodiments, the stabilizer is an organophosphine stabilizer and/or an elastomer.
In one or more embodiments, the organic phosphine is selected from one or more of tricyclohexylphosphine, triphenylphosphine, and trihexylphosphine, more preferably tricyclohexylphosphine.
In one or more embodiments, the elastomer is selected from one or more of thermoplastic elastomers, ethylene propylene rubber, ethylene propylene diene monomer, ABS, ASA and natural rubber materials, more preferably ABS.
In one or more embodiments, the liquid catalyst composition contains from 0.1 to 12 wt% stabilizer, based on the total weight of the liquid catalyst composition.
In one or more embodiments, the stabilizer is an organophosphine present in an amount of 0.1 to 5 weight percent.
In one or more embodiments, the stabilizer is an elastomer and is present in an amount of 0.1 to 12 wt%.
In one or more embodiments, the liquid catalyst composition has a viscosity of 450 mPas or less.
In one or more embodiments, the liquid catalyst composition has a viscosity of 200 mPas or less.
In a second aspect, the present invention provides a cyclic olefin resin composition, which comprises a composition a and a composition B, wherein the composition a contains a cyclic olefin composition, and the composition B contains a liquid catalyst composition according to any one of the embodiments herein.
In one or more embodiments, composition a contains not less than 40 wt% DCPD and 0.5 to 60 wt% TCPD, and optionally a cyclic olefin compound other than DCPD and TCPD.
In one or more embodiments, the cyclic olefin compound other than DCPD and TCPD is selected from cyclooctadiene, ethylidene norbornene, methylcyclopentadiene dimer.
In one or more embodiments, the composition a further comprises an antioxidant.
In one or more embodiments, the antioxidant is selected from one or more of 2, 6-di-tert-butyl-p-methylphenol, tert-butyl-4-hydroxyanisole, 2, 6-di-tert-butyl-p-methylphenol, and resorcinol.
In one or more embodiments, the mass ratio of composition a to composition B is from 10:1 to 550: 1.
In one or more embodiments, the mass ratio of composition a to composition B is from 50:1 to 250: 1.
In a third aspect, the present invention provides a cyclic olefin resin material prepared from the cyclic olefin resin composition according to any of the embodiments herein.
In one or more embodiments, the cyclic olefin resin material has a tensile strength of 50MPa or more, a tensile modulus of 2012MPa or more, and an elongation at break of 5.9% or more.
In a fourth aspect, the present invention provides a method for preparing a thermosetting cycloolefin resin, the method including a step of subjecting a liquid cycloolefin or a liquid cycloolefin composition to a ROMP reaction in the presence of the liquid catalyst composition according to any one of the embodiments herein.
Detailed Description
In order to solve the problems, the ruthenium carbene catalyst is directly dissolved/dispersed in unsaturated acid anhydride containing a C ═ C structure in a molecule and having no more than 20 carbon atoms in the molecule and/or ester containing a C ═ C structure and having no more than 20 carbon atoms in the molecule, so as to form a stable liquid low-viscosity catalyst composition (also called a catalyst system). The catalytic system has good storage stability; when the catalyst composition is used for carrying out ROMP reaction on liquid cycloolefine or a liquid cycloolefine composition, continuous automatic production can be easily realized; furthermore, the dispersion used in the catalytic system does not lead to a reduction in the mechanical properties of the products obtained by the polymerization of cycloolefins. In addition, in the process of preparing the catalytic system, chlorinated paraffin is not required to be introduced to dissolve the catalyst, the use of high-viscosity materials is avoided in the construction process of the catalyst composition, the accuracy and operability of material feeding and mixing in the technological process are improved, and the continuous and automatic production process is more favorably realized. In addition, the resin and the catalyst composition used in the invention can form a stable component without being compounded with an epoxy resin formula, and can be used independently.
Ruthenium carbene catalysts
The ruthenium carbene catalyst refers to a chemical compound containing ruthenium element and a carbene structure, and is commonly used for catalyzing olefin metathesis reaction. The ruthenium carbene catalyst suitable for use in the present invention may be selected from one or more of Grubbs first generation catalysts, Grubbs second generation catalysts and ruthenium carbene compounds represented by formula I or salts thereof.
Herein, the Grubbs first generation catalyst has the following structure:
the Grubbs second generation catalyst has the following structure:
the ruthenium carbene compounds of formula I may be as described in CN 202011520977.8 (the entire content of which is herein incorporated by reference). Specifically, the ruthenium carbene compound of formula I has the following structure:
wherein the content of the first and second substances,
R1and R2Each independently is C4-C18Alkyl or by R1-1Substituted C4-C18An alkyl group; r1-1Is C6-C10An aryl group; cy is cyclohexyl; mes is mesityl represented by the formula (the wavy line indicates the position of attachment to the remainder of the compound of formula I):
in some specific embodiments, the C4-C18 alkyl is substituted with R1-1The C4-C18 alkyl group of the substituted C4-C18 alkyl groups may independently be a C4-C10 alkyl group, preferably a C4-C6 alkyl group, such as a C4 alkyl group, a C5 alkyl group or a C6 alkyl group, further such as an n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl group, preferably an n-butyl or n-hexyl group.
In some specific embodiments, the group R is1-1In the substituted C4-C18 alkyl group, R1-1The number of (B) may be 1,2 or 3, and when 2 or 3, the same or different.
In some specific embodiments, the C6-C10 aryl group can be phenyl or naphthyl.
In some specific embodiments, R1And R2And may independently be n-butyl or n-hexyl.
In some specific embodiments, R1And R2And may independently be a C4-C18 alkyl group.
In some embodiments, R has1And R2May be the same or different.
In some embodiments, the ruthenium carbene compounds of formula I according to the present invention may be selected from any of the following structures:
in some embodiments, the ruthenium carbene catalyst is a Grubbs second generation catalyst, a ruthenium carbene compound I-1 represented by the following structural formula:
in the present invention, the liquid catalyst composition containing the ruthenium carbene catalyst contains 0.5 to 50 wt%, preferably 3 to 40 wt%, more preferably 5 to 30 wt% of the ruthenium carbene catalyst, based on the total weight thereof. In some embodiments, the liquid catalyst composition contains 5 to 15 wt% of the ruthenium carbene catalyst. In some embodiments, the liquid catalyst composition contains from 8 to 15 wt% of a ruthenium carbene catalyst. In some embodiments, the liquid catalyst composition comprising a ruthenium carbene catalyst comprises 5 to 15 wt% (e.g., about 10 wt%) of ruthenium carbene catalyst I-1. In some embodiments, the liquid catalyst composition containing the ruthenium carbene catalyst contains 5 to 15 wt% of Grubbs second generation catalyst.
Unsaturated acid anhydride containing C-C structure and no more than 20 carbon atoms in molecule and/or unsaturated acid anhydride containing C-C structure and no more than 20 carbon atoms in molecule
Esters not exceeding 20
The liquid catalyst composition is prepared by selecting unsaturated acid anhydride containing C ═ C structure and no more than 20 carbon atoms in the molecule and/or ester containing C ═ C structure and no more than 20 carbon atoms in the molecule as a dispersion system (namely solvent) of the ruthenium carbene catalyst. The unsaturated anhydride and ester do not have reactive H capable of being dissociated in the molecule+Or H.a group such as-OH, -COOH, etc.
In the present invention, preferably, the unsaturated acid anhydride having a C ═ C structure and having no more than 20 carbon atoms in the molecule is a cyclic acid anhydride. The cyclic anhydride comprises the following structure:
wherein the wavy line indicates the position at which the structure is attached to the remainder of the cyclic anhydride. The rings in the cyclic anhydride may be bridged, spiro or fused rings, and generally the number of ring atoms of the rings may be in the range of 5 to 15. The ring may optionally contain an additional heteroatom other than anhydride-forming O, the additional heteroatom selected from O, S and N. Preferably, the number of additional heteroatoms is 1,2 or 3. The ring may be optionally substituted, for example with 1 to 6 substituents selected from halogen (including F, Cl, Br and I) and C1-C4 alkyl. Preferably, the ring is an unsaturated ring containing the C ═ C structure. Exemplary unsaturated anhydrides include, but are not limited to, maleic anhydride, 5, 6-dimethyl-3 a,4,7,7 a-tetrahydro-2-benzofuran-1, 3-dione, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, 1,2,5, 6-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, biphenyl anhydride, exo-nadic anhydride, endo-nadic anhydride, exo-furan-maleic anhydride adduct, exo-cyclohexene-maleic anhydride adduct, and the like.
In the present invention, the ester is formed from a fatty acid and a fatty alcohol, and may be a monoester or a polybasic ester. The monoester is an ester of a monocarboxylic acid and a fatty alcohol, or an ester of a monohydric alcohol and a carboxylic acid. The polyester may be an ester of a polybasic organic acid with a fatty acid, or an ester of a polyhydric alcohol with a fatty acid, and has two or more ester groups [ (C (O) -O- ]) in its molecular structure. In the ester of the present invention, at least one of the fatty acid chain and the fatty alcohol chain contains a C ═ C double bond. The number of carbon atoms of the fatty acid chain and the number of carbon atoms of the fatty alcohol chain are such that the total number of carbon atoms of the ester is not more than 20. In a preferred embodiment, at least one of the fatty acid chain and the fatty alcohol chain contains a ring structure, and preferably the C ═ C double bond is located on the ring structure. The ring structure may be a bridged, spiro or fused ring, and may optionally contain a heteroatom selected from O, N and S, the number of heteroatoms may be 1-3. The ring structure may have 3 to 10 ring atoms. Exemplary ring structures include C4-C8 cycloolefins or C4-C8 bridged cycloolefins, such as bicyclo [2.2.1] -2-heptene and cyclohexene. Exemplary fatty acid chains of esters include, but are not limited to, fatty acid chains from 5-norbornene-2, 3-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid, and maleic acid. Exemplary fatty alcohol chains include, but are not limited to, C1-C4 alcohols, such as methanol and ethanol, and the like. In some embodiments, exemplary esters include one or more of dimethyl 5-norbornene-2, 3-dicarboxylate, dimethyl 4-cyclohexene-1, 2-dicarboxylate, methyl 3-cyclohexene-1-carboxylate, and diethyl maleate.
In the present invention, the content of the unsaturated anhydride and/or ester in the liquid catalyst composition of the present invention may be 35 to 99.5 wt%, preferably 70 to 95 wt%. In some embodiments, the unsaturated anhydride and/or ester is present in the liquid catalyst composition of the present invention in an amount of from 85 to 95 weight percent.
In some embodiments, the liquid catalyst composition comprising the ruthenium carbene catalyst comprises 80 to 95 wt% nadic anhydride, for example about 90 wt% nadic anhydride. In some embodiments, the liquid catalyst composition comprising ruthenium carbene catalysts comprises from 85 to 95 weight percent methyl nadic anhydride, for example about 90 weight percent methyl nadic anhydride. In some embodiments, the liquid catalyst composition comprising a ruthenium carbene catalyst comprises a mixture of 10 to 20 wt% nadic anhydride and 60 to 85 wt% methylnadic anhydride, for example, a mixture of about 17 wt% nadic anhydride and about 70 wt% methylnadic anhydride. In other specific embodiments, the liquid catalyst composition comprising the ruthenium carbene catalyst comprises a mixture of 5 to 20 weight percent maleic anhydride, 40 to 70 weight percent 1,2,5, 6-tetrahydrophthalic anhydride, and 15 to 20 weight percent dimethyl 5-norbornene-2, 3-dicarboxylate, such as a mixture of about 8.8 weight percent maleic anhydride, about 59.84 weight percent 1,2,5, 6-tetrahydrophthalic anhydride, and about 17.6 weight percent dimethyl 5-norbornene-2, 3-dicarboxylate; or a mixture of about 18 weight percent maleic anhydride, about 50.4 weight percent 1,2,5, 6-tetrahydrophthalic anhydride, and about 18 weight percent dimethyl 5-norbornene-2, 3-dicarboxylate.
The reason why the unsaturated acid anhydride containing a C ═ C structure and having no more than 20 carbon atoms in the molecule and/or the ester containing a C ═ C structure and having no more than 20 carbon atoms in the molecule are selected to directly dissolve/disperse the ruthenium carbene catalyst is two:
first, the present inventors have found that if the solvent/dispersant used in the catalytic system is too polar, the catalyst activity will be drastically reduced. Therefore, acid anhydride and ester substances with moderate polarity are selected as the solvent/dispersant of the catalytic system, and the catalyst can be ensured to have good catalytic activity on the cycloolefin substances on the premise of fully dissolving/dispersing the catalyst. In the invention, the moderate polarity means that the molecular structure does not have active H which is easy to dissociate in the system+Or H.group (e.g., -OH, -COOH, etc.), unsaturated acid anhydride and ester used in the present invention, will not spontaneously dissociate active H without external stimulus+Or H.
Secondly, when the cycloolefins or the compositions thereof (particularly the cycloolefin composition system mainly comprising DCPD, TCPD and derivatives thereof) are cured by using the ruthenium carbene catalyst, the surface flow mark phenomenon of the products is aggravated by the non-reactive solvent/dispersant in the system, so that the probability of generating defects inside the materials in the curing process is increased. When the catalytic system is constructed, the reactivity of the used dispersion system and the dissolved catalyst is favorable for overcoming the adverse effect on the product performance when the common solvent is used under certain conditions. Therefore, the above requirements can be preferably satisfied by using, as a solvent/dispersant for a catalyst system, an unsaturated acid anhydride having a C ═ C structure in a molecular structure and having no more than 20 carbon atoms in a molecule and/or an ester having a C ═ C structure and having no more than 20 carbon atoms in a molecule.
Optional stabilizers
In some embodiments, the present invention has found that the addition of a stabilizer can inhibit or reduce the reaction of the ruthenium carbene catalyst with the ruthenium carbene catalyst slowly at room temperature or the oligomerization reaction triggered by the stimulation of external accidental factors due to the existence of a C ═ C structure in an anhydride and/or ester, and the oligomerization reaction triggered by the local high-concentration area or the rapid bottom-up phenomenon of the powder/gel catalyst at the initial stage of mixing when the powder/gel catalyst is prepared by adding a low-viscosity solvent/dispersant. For this purpose, a suitable amount of stabilizer can be added to the dispersion system of the present invention before the ruthenium carbene catalyst is mixed into the dispersion system, and the processability during the mixing process can be improved by adjusting the viscosity of the system (e.g.. ltoreq.250 cP, 25 ℃). Thus, in these embodiments, the liquid catalyst composition of the present invention may also contain an appropriate amount of a stabilizer.
Suitable stabilizers in the present invention include, but are not limited to, organophosphine stabilizers and elastomers. Exemplary organophosphines include, but are not limited to, one or more of tricyclohexylphosphine, triphenylphosphine, trihexylphosphine, and phosphine compounds having similar structures, with the preferred organophosphine being tricyclohexylphosphine. Exemplary elastomers include, but are not limited to, one or more of thermoplastic elastomer (POE), ethylene propylene rubber, Ethylene Propylene Diene Monomer (EPDM), ABS, ASA, and natural rubber. The preferred elastomer is ABS. In particular, when the ruthenium carbene catalyst (such as Grubbs second generation catalyst) has low solubility and slow dissolution rate in the dispersion system disclosed by the invention, a proper amount of elastomer is added into the liquid catalyst composition disclosed by the invention, which is helpful for improving the solubility and the dissolution rate of the liquid catalyst composition, so that a stable colloidal dispersion system is obtained, and the catalyst is prevented from being separated out and settled out of the system.
When added, the stabilizer may be present in an amount of 0.1 to 12 wt%, based on the total weight of the liquid catalyst composition. In some embodiments, organic phosphorus is used as a stabilizer, which can be present in the liquid catalyst composition in an amount of from 0.1 to 5 weight percent, such as from 1 to 4 weight percent. In some embodiments, an elastomer is used as a stabilizer, which may be present in the liquid catalyst composition in an amount of from 0.1 to 12 wt%, such as from 1 to 5 wt%. In some embodiments, ABS is used as a stabilizer in an amount of 1 to 3 wt% in the liquid catalyst composition.
Liquid catalyst combinationArticle (A)
The liquid catalyst composition of the invention contains a ruthenium carbene catalyst, an unsaturated acid anhydride containing a C ═ C structure and having no more than 20 carbon atoms in a molecule and/or an ester containing a C ═ C structure and having no more than 20 carbon atoms in a molecule, and optionally a stabilizer. The liquid catalyst composition has low and stable viscosity, and can be used for ROMP reaction of liquid cycloolefine or liquid cycloolefine composition to realize continuous automatic production.
In some embodiments, the liquid catalyst composition of the present invention may contain 35 to 99.5 wt%, preferably 75 to 95 wt%, of the unsaturated anhydride and/or ester, 3 to 40 wt%, preferably 5 to 30 wt%, of the ruthenium carbene catalyst, and optionally a stabilizer.
In some preferred embodiments, the liquid catalyst composition of the present invention comprises 85 to 95 weight percent (e.g., 90 weight percent) nadic anhydride and 5 to 15 weight percent (e.g., about 10 weight percent) ruthenium carbene catalyst I-1. In other preferred embodiments, the liquid catalyst composition of the present invention comprises 15 to 25 weight percent (e.g., about 20 weight percent) nadic anhydride, 65 to 75 weight percent (e.g., about 70 weight percent) methylnadic anhydride, and 5 to 15 weight percent (e.g., about 10 weight percent) ruthenium carbene catalyst I-1. In other preferred embodiments, the liquid catalyst composition of the present invention comprises 15 to 20 weight percent (e.g., about 17 weight percent) nadic anhydride, 65 to 75 weight percent (e.g., about 70 weight percent) methylnadic anhydride, 5 to 15 weight percent (e.g., about 10 weight percent) ruthenium carbene catalyst I-1, and 1 to 5 weight percent (e.g., about 3 weight percent) tricyclohexylphosphine.
Meanwhile, the liquid catalyst composition can also be prepared from Grubbs second generation catalyst and a catalyst system dispersion liquid. In some preferred embodiments, the catalyst system comprises 8 to 12 weight percent (e.g., about 10 weight percent) maleic anhydride, 65 to 70 weight percent (e.g., about 68 weight percent) 1,2,5, 6-tetrahydrophthalic anhydride, 18 to 22 weight percent (e.g., about 20 weight percent) dimethyl 5-norbornene-2, 3-dicarboxylate, and 1 to 3 weight percent (e.g., about 2 weight percent) tricyclohexylphosphine, based on the total weight of the catalyst system dispersion. In other preferred embodiments, the catalyst system comprises 18 to 22 wt% (e.g., about 20 wt%) maleic anhydride, 55 to 60 wt% (e.g., about 56 wt%) 1,2,5, 6-tetrahydrophthalic anhydride, 18 to 22 wt% (e.g., about 20 wt%) dimethyl 5-norbornene-2, 3-dicarboxylate, 1 to 3 wt% (e.g., about 2 wt%) tricyclohexylphosphine, and 1 to 3 wt% (e.g., about 2 wt%) ABS, based on the total weight of the catalyst system dispersion. Wherein the mass ratio of the Grubbs second generation catalyst to the dispersion (containing the unsaturated anhydride and/or ester and optional stabilizer of the invention) is 5-20: 80-95.
It should be noted that in the preparation process of the liquid catalyst composition, the ruthenium carbene catalyst can be pre-dissolved in a small amount of traditional low-viscosity low-boiling point solvent, such as benzene, toluene, xylene, petroleum ether and the like, and then mixed with the solvent/dispersant used in the invention, and after being uniformly mixed, the traditional low-boiling point solvent is removed from the catalytic system by using a certain shaped pump, so that the effect described in the invention can be achieved.
In some embodiments, the liquid catalyst composition of the present invention has a viscosity (25 ℃) of 450 mPas or less, preferably 300 mPas or less, more preferably 150 mPas or less. In some embodiments, the liquid catalyst composition of the present invention has a viscosity (25 ℃) of 50 mPas or less.
Resin composition
The invention provides a cycloolefin resin composition, which comprises a composition A and a composition B, wherein: composition a contained a cyclic olefin and composition B contained a liquid catalyst composition as described herein.
Herein, the cyclic olefin may be a cyclic olefin known in the art for preparing a cyclic olefin resin, including, but not limited to, one or more of DCPD, TCPD, cyclooctadiene, ethylidene norbornene, and methylcyclopentadiene dimer. Preferably, the composition A of the invention contains DCPD and TCPD, wherein, based on the total weight of the composition A, the content of DCPD is more than or equal to 40 wt%, and the content of TCPD can be 0.5-60 wt%. In addition to DCPD and TCPD, other cyclic olefin monomers known in the art to be useful in the preparation of cyclic olefin resins can be used in composition a, including but not limited to one or more of cyclooctadiene, ethylidene norbornene, and methylcyclopentadiene dimer. Preferably, the cycloolefin is a cycloolefin that is liquid at ordinary temperature (25 ℃).
In some embodiments, an antioxidant may also be added to composition a. Antioxidants known in the art for use in the preparation of resins, particularly cyclic olefin resins, are useful in the present invention. Exemplary antioxidants include, but are not limited to, phenolic and/or phenylate antioxidants, such as including one or more of the phenolic or phenylate classes of 2, 6-di-tert-butyl-p-methylphenol, tert-butyl-4-hydroxyanisole, 2, 6-di-tert-butyl-p-methylphenol, resorcinol, and the like. The amount of antioxidant in composition A may be any amount conventionally used in the art, and is exemplified by an amount of 0.1 to 2 wt% based on the total weight of composition A.
In the resin composition, the mass ratio of the composition A to the composition B can be 10:1-550: 1. In some embodiments, the mass ratio of composition a to composition B is from 50:1 to 250: 1.
Cycloolefin resin material and preparation thereof
The invention also provides a cycloolefin resin material which is prepared from the cycloolefin resin composition. In some embodiments, the cyclic olefin resin material has a tensile strength of 50MPa or more, a tensile modulus of 2000MPa or more, and an elongation at break of 5.5% or more. In a preferred embodiment, the cyclic olefin resin material has a tensile modulus ≥ 2010MPa, more preferably ≥ 2020 MPa. In a preferred embodiment, the cyclic olefin resin material has an elongation at break of 6.0% or more, more preferably 6.5% or more.
The cyclic olefin resin material can be prepared using the liquid catalyst composition disclosed herein by methods well known in the art. An exemplary preparation method comprises introducing the above-mentioned composition A and composition B into a mold to react, and the temperature of the mold can be controlled within the range of 40-140 deg.C, preferably 60-100 deg.C. The reaction time may be suitably selected depending on the amount of the reactants. Exemplary reaction times (curing times) may range from 0.1 to 8 hours. Composition a and composition B can be injected into a mold using a RIM apparatus. As previously mentioned, the mass ratio of composition a to composition B may be 10:1 to 550:1, preferably 50:1 to 250: 1.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise indicated, conventional in the art. The starting compounds in the examples are all commercially available.
The methods for measuring the tensile strength, the tensile modulus and the elongation at break of the cycloolefin resin material are all carried out according to the regulations of GB/T2567-2008. The specification of the poured resin plate can meet the test standard.
Example 1
1. Preparation of the cycloolefin composition (composition A): adding 90 parts by mass of DCPD and 10 parts by mass of TCPD into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours, sealing and discharging after heating, and storing the product in a raw material barrel in a nitrogen seal mode.
2. Preparation of the liquid catalyst composition (composition B): under the protection of dry nitrogen atmosphere, 90 parts by mass of nadic anhydride was added to a dry glass kettle, and then 10 parts of ruthenium carbene catalyst I-1 was added under stirring, and stirred at 25 ℃ for 2 hours (stirring speed of 600 rpm). After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
3. Preparation of polycycloolefin resin material: the prepared A, B components are respectively sealed into corresponding charging pots, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then are injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 51MPa, a tensile modulus of 2012MPa and an elongation at break of 6.9%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.13mm (thickness of the resin plate: 4 mm).
Example 2
1. Preparation of the cycloolefin composition (component A): 89.5 parts by mass of DCPD and 10 parts by mass of TCPD are added into a stirring kettle, after the atmosphere in the replacement kettle is high-purity nitrogen, the temperature is raised to 60 ℃, and the stirring is carried out for 2 hours. After the heating, the mixture was cooled to room temperature, and 0.5 part by mass of 2, 6-di-tert-butyl-p-methylphenol (antioxidant ) was added thereto and stirred for 0.5 hour. And after the mixing is finished, the materials are discharged in a sealed way, and the products are stored in a raw material barrel in a nitrogen-sealed way.
2. Preparation of the liquid catalyst composition (component B): under the protection of a dry nitrogen atmosphere, 20 parts by mass of nadic anhydride and 70 parts by mass of methylnadic anhydride were added to a dry glass kettle, and then 10 parts by mass of ruthenium carbene catalyst I-1 was added under stirring, and stirred at 25 ℃ for 2 hours (stirring speed 600 rpm). After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
3. Preparation of polycycloolefin resin material: the prepared A, B components are respectively sealed into corresponding charging pots, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then are injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2024MPa and an elongation at break of 7.0%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.13mm (thickness of the resin plate: 4 mm).
Example 3
1. Preparation of the cycloolefin composition (component A): adding 90 parts by mass of DCPD and 9.5 parts by mass of TCPD into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, and stirring for 2 hours. After the heating, the mixture was cooled to room temperature, and 0.5 part by mass of 2, 6-di-t-butyl-p-methylphenol was added thereto and stirred for 0.5 hour. And after the mixing is finished, the materials are discharged in a sealed way, and the products are stored in a raw material barrel in a nitrogen-sealed way.
2. Preparation of the liquid catalyst composition (component B): under the protection of a dry nitrogen atmosphere, 17 parts by mass of nadic anhydride and 70 parts by mass of methylnadic anhydride were added to a dry glass kettle, then 10 parts by mass of ruthenium carbene catalyst I-1 was added under stirring, stirred at 25 ℃ for 2 hours (stirring speed of 600rpm), and then 3 parts by mass of tricyclohexylphosphine was added to the glass kettle. After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
3. Preparation of polycycloolefin resin material: the prepared A, B components are respectively sealed into corresponding charging pots, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then are injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2026MPa and an elongation at break of 7.1%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.14mm (thickness of the resin plate: 4 mm).
Example 4
1. Preparation of the cycloolefin composition (component A): adding 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours, sealing and discharging after the reaction is finished, and storing the product in a raw material barrel in a nitrogen seal mode.
2. Preparation of the liquid catalyst composition (component B): under the protection of dry nitrogen atmosphere, 90 parts by mass of methylnadic anhydride was added to a dry glass kettle, and then 10 parts of ruthenium carbene catalyst I-1 was added under stirring, and stirred at 25 ℃ for 2 hours (stirring speed of 600 rpm). After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
3. Preparation of polycycloolefin resin material: the formulated A, B components were separately packaged into respective cans, and A, B two streams were mixed using a dedicated RIM apparatus at 150:1 mass ratio, and then injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2044MPa and an elongation at break of 7.3%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.14mm (thickness of the resin plate: 4 mm).
Example 5
1. Preparation of the cycloolefin composition (component A): adding 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours, sealing and discharging after the reaction is finished, and storing the product in a raw material barrel in a nitrogen seal mode.
2. Preparing a liquid catalyst composition dispersion liquid: under the protection of dry nitrogen atmosphere, 10 parts by mass of maleic anhydride, 68 parts by mass of 1,2,5, 6-tetrahydrophthalic anhydride, 20 parts by mass of 5-norbornene-2, 3-dimethyl dicarboxylate, and 2 parts by mass of tricyclohexylphosphine were added to a dry glass kettle, and after sufficient stirring, the mixture was heated to 60 ℃, stirred at this temperature for 2 hours (stirring speed 600rpm), and after sufficient mixing, the mixture was cooled to room temperature.
3. Preparation of the liquid catalyst composition (component B): 12 parts by mass of Grubbs second-generation catalyst were rapidly added under dry nitrogen protection to a reaction vessel containing 88 parts by mass of the prepared dispersion, and vigorously stirred (600rpm) for 1 hour. During the stirring process, the temperature of the material was controlled at 10 ℃. After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
4. Preparation of polycycloolefin resin material: the prepared A, B components are respectively sealed into corresponding charging pots, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then are injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2052MPa, and an elongation at break of 5.9%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.12mm (thickness of the resin plate: 4 mm).
Example 6
1. Preparation of the cycloolefin composition (component A): adding 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours, sealing and discharging after the reaction is finished, and storing the product in a raw material barrel in a nitrogen seal mode.
2. Preparing a liquid catalyst composition dispersion liquid: under the protection of a dry nitrogen atmosphere, 20 parts by mass of maleic anhydride, 56 parts by mass of 1,2,5, 6-tetrahydrophthalic anhydride, 20 parts by mass of 5-norbornene-2, 3-dicarboxylic acid dimethyl ester, 2 parts by mass of tricyclohexylphosphine, and 2 parts by mass of ABS were added to a dry glass kettle, and after thoroughly stirring, the mixture was heated to 80 ℃ and further stirred at this temperature for 12 hours (stirring speed 600rpm), after thoroughly mixing, the mixture was cooled to room temperature (viscosity: 150 mPas, 25 ℃).
3. Preparation of the liquid catalyst composition (component B): 10 parts by mass of Grubbs second-generation catalyst were rapidly added under dry nitrogen protection to a reaction vessel containing 90 parts by mass of the prepared dispersion, and vigorously stirred (600rpm) for 1 hour. During the stirring process, the temperature of the material was controlled at 10 ℃. After the stirring, the mixture was discharged under sealed conditions, and the obtained material (viscosity: 150 mPas, 25 ℃ C.) was stored in a raw material tank under nitrogen-sealed conditions.
4. Preparation of polycycloolefin resin material: the formulated A, B components were separately packaged into respective cans, and A, B two streams were mixed using a dedicated RIM apparatus at 150:1, and injecting the mixture into a mold at the temperature of 80 ℃ for 3 hours. The tensile strength of the obtained material is 53MPa, the tensile modulus is 2082MPa, and the elongation at break is 6.9%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.10mm (thickness of the resin plate: 4 mm).
Comparative example 1 (with DCPD as component A)
1. Preparation of the liquid catalyst composition (component B): under the protection of dry nitrogen atmosphere, 90 parts by mass of nadic anhydride is added into a dry glass kettle, 10 parts of ruthenium carbene catalyst I-1 is added under the condition of stirring, and the mixture is stirred for 2 hours at 25 ℃. After the stirring is finished, the mixture is discharged in a sealed manner, and the obtained material (the viscosity is less than 10mPa & s, 25 ℃) is stored in a raw material barrel in a nitrogen-sealed manner.
2. Preparation of polycycloolefin resin material: the DCPD is used as a component A, A, B components are respectively sealed into corresponding charging pots, heat preservation is carried out for 1 hour at 35 ℃, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then injected into a mould, the temperature of the mould is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 48MPa, a tensile modulus of 1851MPa and an elongation at break of 5.4%.
Comparative example 2 (toluene as solvent)
1. Preparation of the cycloolefin composition (component A): adding 75 parts by mass of DCPD, 10 parts by mass of TCPD and 15 parts by mass of methylcyclopentadiene dimer into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours, sealing and discharging after the reaction is finished, and storing the product in a raw material barrel in a nitrogen seal mode.
2. Preparation of the liquid catalyst composition (component B): before the material preparation was performed, 10 parts by mass of Grubbs' second generation catalyst was dissolved in 90 parts by mass of toluene.
3. Preparation of polycycloolefin resin material: the prepared A, B components are respectively sealed into corresponding charging pots, A, B two material flows are mixed according to the mass ratio of 150:1 by using special RIM equipment and then are injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 50MPa, a tensile modulus of 1998MPa and an elongation at break of 5.8%. The resulting sample was smooth on one side and had a large number of grooves on the other side, with an average depth of 0.25mm (thickness 4 mm).
Example 7
1. Component a and component B were formulated separately as in example 3 above. Wherein component B was formulated 6 months in advance and stored at room temperature.
2. Preparation of polycycloolefin resin material: the freshly prepared component A and the component B stored for 6 months are respectively sealed into corresponding charging pots, A, B two streams are mixed according to the mass ratio of 150:1 by using special RIM equipment and then injected into a mold, the temperature of the mold is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2012MPa and an elongation at break of 7.1%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.13mm (thickness of the resin plate: 4 mm).
Comparative example 3
1. Component A and component B were prepared according to the procedure of comparative example 2. Wherein, the component B is prepared 24 hours in advance and stored at room temperature.
2. Respectively packaging the component A and the component B which is placed for 24 hours in corresponding charging pots, mixing the A, B two streams according to the mass ratio of 150:1 by using a special RIM device, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours. After opening the mould, the material was found to be not completely solidified and to be in the form of gel.
Example 8
1. Component a and component B were formulated separately as in example 5 above. Wherein component B was formulated 6 months in advance and stored at room temperature.
2. Preparation of polycycloolefin resin material: the freshly prepared component A and the component B stored for 6 months (viscosity <10mPa & s, 25 ℃) are respectively sealed into corresponding charging pots, A, B two streams are mixed according to the mass ratio of 150:1 by using a special RIM device and then injected into a mold, the mold temperature is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 52MPa, a tensile modulus of 2049MPa and an elongation at break of 6.1%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.12mm (thickness of the resin plate: 4 mm).
Example 9
1. Component a and component B were formulated separately as in example 6 above. Wherein component B was formulated 6 months in advance and stored at room temperature.
2. Preparation of polycycloolefin resin material: the freshly prepared component A and the component B stored for 6 months (viscosity: 152 mPas, 25 ℃) are respectively sealed into corresponding charging pots, A, B two streams are mixed according to the mass ratio of 150:1 by using a special RIM device and then injected into a mold, the mold temperature is 80 ℃, and the curing time is 3 hours. The resulting material had a tensile strength of 53MPa, a tensile modulus of 2075MPa and an elongation at break of 7.3%. The resulting resin plate had a smooth side and a small amount of flow marks on the other side, the average depth of the flow marks being 0.09mm (thickness of the resin plate: 4 mm).
Comparison of examples 1 and 4 with comparative example 1 shows that when TCPD is added to component A or TCPD and a third cycloolefin monomer are added simultaneously, the performance of the prepared resin material in terms of tensile strength and tensile modulus can be improved; from a comparison of example 5 with comparative example 2, it can be seen that when the same cycloolefin composition is cured, the resulting resin product has a higher tensile modulus and tensile strength using the catalyst composition disclosed in the present invention compared to a toluene solution of the conventional Grubbs's second generation catalyst. As can be seen from the comparison of examples 3 and 7 with comparative examples 2 to 3, the catalyst system for the polymerization of a liquid cyclic olefin composition disclosed in the present invention has good storage stability, and can overcome the problem that the conventional catalyst solution system is easily deactivated during storage. The storage stability of the catalytic system disclosed in the present invention is further demonstrated by a comparison of the results of examples 5,6 and examples 8, 9. Meanwhile, the comparison of the results of examples 1 to 6 and comparative example 2 also shows that the surface flow mark problem of the molding material can be effectively improved by using the catalyst composition disclosed by the invention.
Claims (17)
1. A liquid catalyst composition comprising a ruthenium carbene catalyst, wherein the liquid catalyst composition comprises a ruthenium carbene catalyst, a solvent and optionally a stabilizer, wherein the solvent comprises an unsaturated acid anhydride having a C ═ C structure and having no more than 20 carbon atoms in a molecule and/or an ester having a C ═ C structure and having no more than 20 carbon atoms in a molecule.
2. The liquid catalyst composition of claim 1, wherein the ruthenium carbene catalyst is selected from the group consisting of:
and a ruthenium carbene compound represented by the following formula I:
in the formula, R1And R2Each independently is C4-C18 alkyl or substituted with R1-1Substituted C4-C18 alkyl; r1-1Is a C6-C10 aryl group; mes is mesityl; cy is cyclohexyl.
3. The liquid catalyst composition of claim 2,
the C4-C18 alkyl is substituted by R1-1The C4-C18 alkyl group of the substituted C4-C18 alkyl groups may independently be a C4-C10 alkyl group;
and/or the said quilt R1-1In the substituted C4-C18 alkyl group, R1-1The number of (B) is 1,2 or 3, and when 2 or 3, R is1-1The same or different;
and/or, the C6-C10 aryl is phenyl or naphthyl;
and &Or, said R1And R2The same or different.
4. The liquid catalyst composition of claim 3,
the C4-C18 alkyl is substituted by R1-1The C4-C18 alkyl group of the substituted C4-C18 alkyl group is independently a C4-C6 alkyl group, such as a C4 alkyl group, a C5 alkyl group or a C6 alkyl group, and further such as an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group or a n-hexyl group, preferably an n-butyl group or a n-hexyl group;
and/or, R1And R2Independently a C4-C18 alkyl group.
5. The liquid catalyst composition of claim 2, wherein the ruthenium carbene compound of formula I is of any of the following structures:
6. the liquid catalyst composition of claim 1,
the unsaturated anhydride is a cyclic anhydride comprising the structure:
wherein the wavy line indicates the position at which the structure is attached to the remainder of the cyclic anhydride; preferably, the rings in the cyclic anhydride are bridged, spiro or fused rings, optionally containing an additional heteroatom in the ring other than the anhydride-forming O, the additional heteroatom being selected from O, S and N, and the ring being optionally substituted with 1-6 substituents selected from halogen and C1-C4 alkyl;
the ester is a mono-or poly-ester, at least one of the fatty acid chain and the fatty alcohol chain forming the ester containing a C ═ C double bond; preferably, at least one of the fatty acid chain and the fatty alcohol chain contains a ring structure; preferably, the ring structure is a bridged, spiro or fused ring; preferably, the ring structure is an unsaturated ring containing the C ═ C double bond.
7. The liquid catalyst composition of claim 6,
the ring in the cyclic anhydride is an unsaturated ring containing the structure of C ═ C;
the ring structure of the ester includes C4-C8 cycloolefins or C4-C8 bridged cycloolefins, such as bicyclo [2.2.1] -2-heptene and cyclohexene; preferably, the fatty acid chains of the esters are derived from the fatty acid chains of 5-norbornene-2, 3-dicarboxylic acid, 4-cyclohexene-1, 2-dicarboxylic acid, 3-cyclohexene-1-carboxylic acid and maleic acid; preferably, the fatty alcohol chain of the ester is a fatty acid chain of a C1-C4 alcohol;
preferably, the unsaturated anhydride and/or ester is selected from the group consisting of maleic anhydride, 5, 6-dimethyl-3 a,4,7,7 a-tetrahydro-2-benzofuran-1, 3-dione, bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylic anhydride, 1,2,5, 6-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, biphenyl anhydride, exo-nadic anhydride, endo-nadic anhydride, exo-furan-maleic anhydride adduct, exo-cyclohexene-maleic anhydride adduct, dimethyl 5-norbornene-2, 3-dicarboxylate, 4-cyclohexene-1, one or more of dimethyl 2-dicarboxylate, methyl 3-cyclohexene-1-carboxylate and diethyl maleate.
8. The liquid catalyst composition of claim 1,
the liquid catalyst composition contains 0.5 to 50 wt%, preferably 3 to 40 wt%, more preferably 5 to 30 wt% of a ruthenium carbene catalyst, based on the total weight of the liquid catalyst composition; and/or
The liquid catalyst composition contains from 35 to 99.5 wt%, preferably from 75 to 95 wt%, of the unsaturated anhydride and/or ester, based on the total weight of the liquid catalyst composition.
9. The liquid catalyst composition of claim 1, wherein the stabilizer is an organophosphine stabilizer and/or an elastomer;
preferably, the organic phosphine is selected from one or more of tricyclohexylphosphine, triphenylphosphine and trihexylphosphine, more preferably tricyclohexylphosphine;
preferably, the elastomer is selected from one or more of thermoplastic elastomers, ethylene propylene rubber, ethylene propylene diene monomer, ABS, ASA and natural rubber materials, more preferably ABS.
10. The liquid catalyst composition of claim 1 or 9, wherein the liquid catalyst composition comprises from 0.1 to 12 wt% of a stabilizer, based on the total weight of the liquid catalyst composition;
preferably, the stabilizer is organic phosphine, and the content of the organic phosphine is 0.1-5 wt%;
preferably, the stabilizer is an elastomer and is present in an amount of 0.1 to 12 wt%.
11. The liquid catalytic system composition of claim 1, wherein the liquid catalyst composition has a viscosity of 450 mPa-s or less, preferably 200 mPa-s or less.
12. A cycloolefin resin composition, characterized in that the cycloolefin resin composition comprises:
composition A: a cycloolefin-containing composition;
composition B: comprising the liquid catalyst composition according to any one of claims 1 to 11.
13. The cyclic olefin resin composition as claimed in claim 12, wherein composition a contains not less than 40 wt% of DCPD and 0.5 to 60 wt% of TCPD, and optionally a cyclic olefin compound other than DCPD and TCPD; preferably, the cyclic olefin compound is selected from cyclooctadiene, ethylidene norbornene, methylcyclopentadiene dimer.
14. The cyclic olefin resin composition according to any of claims 12 to 13, wherein the composition a further comprises an antioxidant; preferably, the antioxidant is a phenolic and/or phenylate antioxidant, preferably selected from one or more of 2, 6-di-tert-butyl-p-methylphenol, tert-butyl-4-hydroxyanisole, 2, 6-di-tert-butyl-p-methylphenol and resorcinol.
15. The cyclic olefin resin composition according to any one of claims 12 to 14, wherein the mass ratio of composition a to composition B is from 10:1 to 550:1, preferably from 50:1 to 250: 1.
16. A cycloolefin resin material produced from the cycloolefin resin composition according to any one of claims 12 to 15; preferably, the tensile strength of the cycloolefin resin material is more than or equal to 50MPa, the tensile modulus is more than or equal to 2000MPa, and the elongation at break is more than or equal to 5.5 percent.
17. A method for preparing a thermosetting cycloolefin resin, characterized by comprising the step of subjecting a liquid cycloolefin or a liquid cycloolefin composition to a ROMP reaction in the presence of the liquid catalyst composition according to any one of claims 1 to 11.
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