CN112661884B - Composition, resin material and preparation method thereof - Google Patents
Composition, resin material and preparation method thereof Download PDFInfo
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- CN112661884B CN112661884B CN202011542553.1A CN202011542553A CN112661884B CN 112661884 B CN112661884 B CN 112661884B CN 202011542553 A CN202011542553 A CN 202011542553A CN 112661884 B CN112661884 B CN 112661884B
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Abstract
The invention discloses a composition, a resin material and a preparation method thereof. The invention specifically discloses a composition, which comprises the following components in parts by weight: 60-100 parts of dicyclopentadiene and 0.01-35 parts of catalyst composition; the catalyst composition comprises a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5% -65%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin. The composition of the invention can be stored for a long time, and the resin material prepared from the composition has good mechanical properties such as tensile strength, tensile modulus and elongation at break.
Description
Technical Field
The invention relates to a composition, a resin material and a preparation method thereof.
Background
It is well known that metal carbene complexes of ruthenium, molybdenum, tungsten, etc. have catalytic effects on olefin metathesis reactions. In the preparation process of the polydicyclopentadiene polymer, a double-component tungsten-molybdenum catalytic system or a ruthenium metal carbene catalytic system is usually adopted to realize the cutting and recombination of olefin carbon-carbon double bonds to form an crosslinked network structure. The thermosetting resin material has the excellent properties of light weight, high strength, impact resistance, corrosion resistance and the like, and is successfully applied to the fields of engineering machinery, light automobiles, chlor-alkali industry and the like.
At present, the polydicyclopentadiene composite material prepared based on a tungsten-molybdenum catalytic system has a resin system which is mostly a double-component feed liquid A and a double-component feed liquid B, each storage tank is stored under a nitrogen seal, and the feed liquid is prepared into a molded product through a reaction injection molding process (RIM). The forming process needs to block oxygen and moisture to ensure the activity of the catalyst and the stable quality of the product, the requirement on reaction forming conditions is higher, the filler, long fiber or continuous fiber is not easy to be added to prepare the structurally reinforced composite material or the functionally modified product, and the popularization range of the polydicyclopentadiene material is greatly limited.
In addition, carbene complexes centered on ruthenium metal are also commonly used as polydicyclopentadiene reaction catalysts, and generally have higher catalytic activity and stability. The catalytic system has simple synthesis process, stable structure, good functional group applicability and low requirement on reaction conditions, and can catalyze the reaction in the presence of impurities such as oxygen, water and the like, thereby becoming a favorable development direction for the application technology development of polydicyclopentadiene. However, the existing ruthenium catalyst system can not realize continuous automatic production for the following reasons:
1. the storage period is short: the existing commercialized ruthenium carbene catalytic system can only be stored for a long time at low temperature in a solid state, is quickly decomposed when being dissolved in common solvents to prepare solution, is difficult to store for a long time, can only be prepared and used at present, cannot be used for a continuous production line, and otherwise, the problems that the equipment cannot be solidified or blocked due to severe reaction caused by inactivation occur.
2. The mixture ratio is very different: the existing commercial ruthenium catalyst system can be prepared and used after being liquefied by adding a solvent, but other components (dissolution or toxicity causes catalyst inactivation) cannot be added, so that the ratio of dicyclopentadiene to the liquid catalyst is usually over 100.
3. Poor compatibility: the existing commercial ruthenium carbene catalytic system polydicyclopentadiene and epoxy and other resin system compound products have the advantages of obvious phase separation, hard and brittle products, low strength, obvious defects and difficult popularization and use.
Therefore, how to overcome the technical defects that the requirement of the anhydrous and anaerobic reaction molding condition of the tungsten-molybdenum catalytic system is high, the difficulty of functional modification or structural enhancement is high, and the long-term storage and continuous production of the ruthenium solid catalyst in the solution are difficult becomes a key for further promoting the development of polydicyclopentadiene and the application technology thereof.
Chinese patent application CN106243279A discloses a multicolor, aging-resistant and spray-free polydicyclopentadiene composite material, and a preparation method and application thereof, the invention is based on a ruthenium carbene catalyst, and a certain amount of copolymer, functional filler, environment-friendly color paste or high-mesh toner is added into a dicyclopentadiene system to prepare the spray-free polydicyclopentadiene composite material, and the product has good appearance color and balanced mechanical properties, and is mainly applied to the field of bathrooms. However, the ruthenium carbene solid catalyst in the technology is mixed with a cosolvent or other components and molded by a single-component RIM glue injection process, so that the storage period of the raw materials is short, the reaction activity is obviously reduced, the ruthenium carbene solid catalyst needs to be prepared in the actual production, and the requirement of continuous production is difficult to meet.
Chinese patent CN1027509C provides a method for preparing thermosetting polymer, in which dicyclopentadiene monomer is respectively and uniformly mixed with metathesis catalyst and cocatalyst, and a certain amount of adjuvant, filler and the like are added, and then the polydicyclopentadiene composite material is prepared by two-component reaction injection molding. However, the catalytic system is a metal carbene complex such as tungsten, molybdenum and tantalum, the bi-component feed liquid needs to be subjected to ring-opening polymerization reaction under anhydrous and oxygen-free conditions in the reaction process, the forming conditions are harsh, the process adaptability is poor, the addition of high-content filler or modification auxiliary agent is difficult to realize, and the application of the technology is limited.
Disclosure of Invention
The invention aims to provide a composition, a resin material and a preparation method thereof. The composition of the invention can be stored for a long time, and the resin material prepared from the composition has good mechanical properties such as tensile strength, tensile modulus and elongation at break.
The invention provides a composition, which comprises the following components in parts by weight: 60-100 parts of dicyclopentadiene and 0.01-35 parts of catalyst composition;
the catalyst composition comprises a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5-65%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin;
wherein R is 1 And R 2 Independently is C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 An alkyl group;
R 1-1 independently is C 6 -C 10 And (4) an aryl group.
In a certain embodiment, some of the resin compositions are defined as follows, and in the undefined cases and other embodiments (hereinafter, referred to as "embodiments"), the chlorinated paraffin preferably has a chlorine content of 5% to 60%, for example, 5%, 42%, 52% or 60%, and the chlorine content is a percentage of the mass of chlorine atoms to the mass of the chlorinated paraffin.
In a certain embodiment, the amount concentration of the ruthenium carbene compound represented by formula I or a salt thereof in the chlorinated paraffin may be 0.08mol/L to 0.7mol/L, preferably 0.1mol/L to 0.6mol/L, such as 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.55mol/L, or 0.6mol/L.
In a certain embodiment, said C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl may independently be C 4 -C 10 Alkyl, preferably C 4 -C 6 Alkyl radicals, e.g. C 4 Alkyl radical, C 5 Alkyl or C 6 Alkyl, for example, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, more preferably n-butyl or n-hexyl.
In one embodiment, the quilt R 1-1 Substituted C 4 -C 18 In the alkyl radical, R 1-1 The number of (B) is 1, 2 or 3, and when 2 or 3, they are the same or different.
In a certain embodiment, said C 6 -C 10 Aryl may be phenyl or naphthyl.
On one handIn the scheme, R 1 And R 2 And may independently be n-butyl or n-hexyl.
In a certain embodiment, R 1 And R 2 Can independently be C 4 -C 18 An alkyl group.
In a certain embodiment, R 1 And R 2 May be the same or different.
In a certain scheme, the ruthenium carbene compound shown in the formula I can be any one of the following structures,
in one embodiment, the catalyst composition can be composed of a ruthenium carbene compound or a salt thereof as shown in formula I, and chlorinated paraffin; the ruthenium carbene compound and the chlorinated paraffin shown in the formula I are as described in any scheme.
In one embodiment, the catalyst composition may be any combination of the following:
combination A1:
and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 5%, 42%, 52% or 60%;
combination A2:
and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 5%, 42%, 52% or 60%;
combination A3:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%;
combination A4:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 42%; />
Combination A5:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%;
combination A6:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 60%;
combination A7:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%.
In one embodiment, the catalyst composition may be any combination of the following:
combination B1:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination B2:
and chlorinated paraffin having a chlorine content of 42%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;
combination B3:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.35mol/L; />
Combination B4:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin was 0.6mol/L;
combination B5:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination B6:
and chlorinated paraffin having a chlorine content of 42%>
The amount concentration of the substance in the chlorinated paraffin was 0.25mol/L;
combination B7:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;
combination B8:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin was 0.6mol/L;
combination B9:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L; />
Combination B10:
and chlorinated paraffin having a chlorine content of 42%>
The mass concentration of the substance in the chlorinated paraffin was 0.35mol/L;
combination B11:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration in the chlorinated paraffin was 0.55mol/L;
combination B12:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin is 0.2mol/L;
combination B13:
and chlorinated paraffin having a chlorine content of 52%,
the amount concentration of the substance in the chlorinated paraffin was 0.35mol/L.
In a certain scheme, the purity of the dicyclopentadiene can be more than or equal to 90%, and preferably, the purity is more than or equal to 98%.
In one embodiment, the dicyclopentadiene is preferably used in an amount of 65 to 99.95 parts by weight, for example 65 parts, 75 parts, 90 parts, or 99.95 parts.
In one embodiment, the catalyst composition is preferably used in an amount of 0.03 to 33 parts, for example 0.04 parts, 12.59 parts, 13.64 parts, or 32.5 parts, by weight.
In one embodiment, the composition may further comprise one or more of comonomers, functional fillers and auxiliaries.
The comonomer may be a comonomer conventional in the art, and may be one or more of norbornene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene, propylene, isoprene, styrene, butadiene, methyl-5-norbornene-2, 3-dicarboxylic anhydride, t-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-carbaldehyde and 5-norbornene-2-methanol, preferably one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and t-butyl 5-norbornene-2-carboxylate.
The comonomers can be used in amounts of 1 to 20 parts by weight, and also 1 to 17 parts by weight, for example 1.89 parts, 7.38 parts or 16.36 parts.
The functional filler can be conventional functional filler in the field, and can also be one or more of graphite powder, mica powder, montmorillonite, titanium dioxide, silicon dioxide, glass fiber, basalt fiber, carbon fiber, polyethylene fiber and aramid fiber, and preferably glass fiber and/or graphite powder.
The functional filler may be used in an amount of 3 to 20 parts by weight, or 3 to 7 parts by weight, for example 5 parts by weight.
The auxiliary agent can be an auxiliary agent which is conventional in the field, and can be one or more of a polymerization regulator, an anti-aging agent, a coupling agent, a toner, a heat stabilizer, a flame retardant and a mold release agent, and is preferably one or more of an anti-aging agent, a coupling agent and a toner.
The polymerization regulator can be a polymerization regulator conventional in the field, and can be one or more of triphenylphosphine, triethyl phosphite, tributyl phosphite, ethylene glycol dimethyl ether, benzophenone and isopropyl ether, and triphenylphosphine and/or triethyl phosphite are preferred. The polymerization regulators may be used in amounts customary in the art, in particular from 7 to 13 parts, for example 10 parts, by weight.
The anti-aging agent can be an anti-aging agent which is conventional in the field, and can be one or more of 2, 6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, tinuvin 571, tinuvin 765, tinuvin B75, tinuvin B88, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531 and UV-770, preferably one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone. The anti-aging agent may be used in an amount of 1 to 5 parts, for example 3.69 parts, based on the parts by weight, as is conventional in the art.
The coupling agent may be a coupling agent conventional in the art, and may be a silane coupling agent, such as silane coupling agent a172. The coupling agent may be used in amounts conventional in the art, and may be used in amounts of 1 to 3 parts, for example 1.26 parts, by weight.
The toner may be a toner as is conventional in the art. The toner may be used in amounts conventional in the art, and may be used in amounts of 1 to 3 parts, for example 1.26 parts, by weight.
The heat stabilizer may be a heat stabilizer conventional in the art. The heat stabilizer may be used in an amount conventional in the art, in parts by weight.
The flame retardant may be one conventional in the art. The amount of the flame retardant may be an amount conventionally used in the art, in parts by weight.
The release agent may be a release agent conventional in the art. The amount of the release agent can be the amount which is conventional in the field according to the weight part.
In one embodiment, the composition may be any combination of:
combination C1: dicyclopentadiene and a catalyst composition;
a combination C2: dicyclopentadiene, catalyst composition and comonomer;
combination C3: dicyclopentadiene, catalyst compositions, comonomers and age resisters;
combination C4: dicyclopentadiene, catalyst compositions, comonomers, functional fillers and polymerization regulators;
a combination C5: dicyclopentadiene, a catalyst composition, a comonomer, a functional filler, a coupling agent and a toner;
the definition of the dicyclopentadiene, the catalyst composition, the comonomer, the functional filler, the age resister, the coupling agent and the toner is as defined in any one of the above schemes.
In one embodiment, the composition may be any combination of:
combination D1: 65-99.95 parts of dicyclopentadiene and 0.03-33 parts of catalyst composition;
combination D2: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer and 1-5 parts of anti-aging agent;
combination D3: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler and 7-13 parts of polymerization regulator;
combination D4: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler, 1-3 parts of coupling agent and 1-3 parts of toner;
combination D5: 65-99.95 parts of dicyclopentadiene and 0.03-33 parts of catalyst composition; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%;
combination D6: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer and 1-5 parts of age resister; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; the comonomer is one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and 5-norbornene-2-carboxylic acid tert-butyl ester; the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone;
combination D7: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler and 7-13 parts of polymerization regulator; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; the comonomer is one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and 5-norbornene-2-carboxylic acid tert-butyl ester; the functional filler is glass fiber and/or graphite powder; the polymerization regulator is triphenyl phosphorus and/or triethyl phosphite;
combination D8: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler, 1-3 parts of coupling agent and 1-3 parts of toner; the catalyst composition is
And chlorinated paraffin with a chlorine content of 52%; the functional filler is glass fiber and/or graphite powder; the coupling agent is a silane coupling agent A172;
combination D9: 65 parts of dicyclopentadiene and 32.5 parts of catalyst composition; the catalyst composition is
And chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D10: 99.95 parts of dicyclopentadiene, 0.04 part of catalyst composition,7.38 parts of ethylene and 3.69 parts of Tinuvin B; the catalyst composition is
And chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D11: 75 parts of dicyclopentadiene, 13.64 parts of catalyst composition, 16.36 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 5 parts of graphite powder and 10 parts of triphenyl phosphorus; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; />
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D12: 80 parts of dicyclopentadiene, 12.59 parts of catalyst composition, 1.89 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 5 parts of glass fiber, 1.26 parts of silane coupling agent A and 1.26 parts of toner; the catalyst composition is
And chlorinated paraffin having a chlorine content of 52%>
The amount concentration of the substance in the chlorinated paraffin was 0.3mol/L.
The invention provides a resin material which is prepared by taking the composition of any scheme as a raw material.
In one embodiment, the epoxy resin and the dicyclopentadiene are preferably cross-linked and polymerized to form an interpenetrating network structure.
The invention provides a preparation method of a resin material, which comprises the following steps: the composition of any scheme is taken as a raw material, dicyclopentadiene and the catalyst composition are uniformly mixed, one or more of a comonomer, a functional filler and an auxiliary agent are optionally added, and the mixture is cured and molded to obtain the resin material.
In one embodiment, the preparation method can adopt RIM process.
In one embodiment, the conditions and operations of the RIM process may be those conventional in the art, and may further comprise the steps of:
(1) Taking dicyclopentadiene as A liquid, and optionally adding one or more of functional filler, comonomer and auxiliary agent;
(2) Taking the catalyst composition as a liquid B, and optionally adding one or more of functional filler, comonomer and auxiliary agent;
(3) Introducing the solution A and the solution B into a material storage system for later use;
(4) The solution A and the solution B are subjected to reaction injection molding in RIM equipment;
(5) And curing to obtain the resin material.
In one embodiment, in step (3), the storage system may be a storage tank of a RIM apparatus.
In a certain scheme, in the step (3), the temperature of the material storage system can be-10 ℃ to 40 ℃, and is preferably-5 ℃ to 25 ℃.
In one embodiment, in step (4), the mass ratio of the solution a to the solution B may be 1.
In one embodiment, in step (4), the solution a and the solution B may be mixed and injected into a mold on line to complete reaction injection molding.
In one embodiment, in step (4), the injection speed of the reaction injection molding may be 200mL/min to 100L/min, preferably 200mL/min to 2000mL/min, such as 200mL/min, 500mL/min or 2000mL/min.
In one embodiment, in step (4), the injection pressure for the reaction injection molding may be 0.1 to 20bar, preferably 1 to 15bar, such as 2bar, 6bar or 15bar.
In one embodiment, in step (5), the temperature for curing may be 60 to 120 ℃, preferably 70 to 100 ℃, for example 80 ℃.
In one embodiment, in step (5), the curing time may be 1-120min, for example, 2h.
The invention also provides a resin material prepared by the preparation method.
In the present invention, "min" means minutes, "h" means hours, "and" ° c "means degrees celsius, unless otherwise specified.
Unless otherwise defined, the terms used in the present invention have the following meanings:
in the invention, the ruthenium carbene compound shown as the formula I or the salt thereof can have one or more chiral carbon atoms, so that optical purity isomers, such as pure enantiomers, racemes or mixed isomers, can be obtained by separation. Pure single isomers can be obtained by separation methods in the art, such as chiral crystallization to form salts, or by chiral preparative column separation.
In the invention, if stereoisomers exist in the ruthenium carbene compound or the ruthenium carbene salt shown in the formula I, the ruthenium carbene compound or the ruthenium carbene salt can exist in the form of a single stereoisomer or a mixture (such as raceme) of the single stereoisomer. The term "stereoisomer" refers to either a cis-trans isomer or an optical isomer. The stereoisomers can be separated, purified and enriched by an asymmetric synthesis method or a chiral separation method (including but not limited to thin layer chromatography, rotary chromatography, column chromatography, gas chromatography, high pressure liquid chromatography and the like), and can also be obtained by chiral resolution in a mode of forming bonds (chemical bonding and the like) or salifying (physical bonding and the like) with other chiral compounds and the like. The term "single stereoisomer" means that the mass content of one stereoisomer of the compound of the invention with respect to all stereoisomers of the compound is not less than 95%.
The term "salt" includes salts prepared by reacting a compound of the invention with an acid, for example: hydrochloride, hydrobromide, sulfate, and the like.
The term "alkyl" refers to a straight or branched chain alkyl group having the indicated number of carbon atoms. Such as C 1 -C 6 Alkyl radicalIs a straight or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl and the like.
The term "aryl" refers to a hydrocarbon radical having aromatic character, such as C 6 -C 10 Aryl, examples of which include phenyl or naphthyl.
In the present invention, the open expression "including" can be converted into the closed expression "consisting of 8230 \8230;.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The catalyst composition in the composition is convenient to use and does not need to be prepared at present.
(2) The catalyst composition in the composition has long storage period, and can still maintain the original catalytic activity after being stored for 6 months.
(3) The composition can be stored for a long time, and the mechanical property of the prepared resin material is not obviously changed after the composition is stored for 6 months.
(4) The resin material prepared by the invention has good mechanical properties such as tensile strength, tensile modulus and elongation at break.
(5) The catalyst composition is in liquid state, so that the production process is suitable for more processes, such as two-component RIM process. Compared with a single-component RIM process, in the double-component RIM process, feed liquid can be stored separately, the storage period is prolonged, and the method is suitable for industrial continuous production.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The instruments and materials involved in the examples are described below:
NMR hydrogen and carbon spectra were obtained using a Bruker AV 400 (400 MHz) instrument. Chemical shifts are expressed in ppm with TMS as internal standard. Recording chemical shifts, splits (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad) and coupling constants (J, unit: hz)
The used solvents such as column chromatography silica gel, diatomaceous earth, dichloromethane, tetrahydrofuran, etc. are commercially available from Schench Biochemical technology Ltd of Tianjin. CDC1 for testing 3 Is available from Shanghai cypress card Co. (PCy) 3 ) 2 C1 2 Ru = CHPh (1) was purchased from tianjin kayverdachi ltd.
Tetrahydrofuran is obtained by distilling after sodium reflux is carried out under the protection of nitrogen until benzophenone solution turns blue; dichloromethane is obtained by calcium hydride treatment and distillation under the protection of nitrogen.
Example 1: synthesis of catalyst 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (4, 5-dibutylimidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium (I-1) containing butyl substituent
The synthesis of the catalyst I-1 containing the butyl substituent comprises the following steps:
1) Preparation of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9)
To a 500mL three-necked flask equipped with a dropping funnel, 3.73mL of an aqueous glyoxal (8) solution (40%) and 80mL of methanol were sequentially added, and the mixture was stirred to dissolve the glyoxal. To the dropping funnel was added 9.12mL of m-trimethylamine (7), 10mL of methanol, and slowly added dropwise to the flask. The reaction solution was stirred for 12 hours while controlling the temperature to about 22 ℃. In this process, a bright yellow precipitate was gradually precipitated from the reaction solution. After the reaction is finished, filtering the reaction liquid to obtain yellow solid, washing the solid with water for three times, washing the solid with methanol for one time, and drying the solid in vacuum to obtain a yellow crystalline product 9. And 6 weight portions.5g, yield 70%. Calcd (found) for C 20 H 24 N 2 ；C,82.15(82.12)；H,8.27(8.20). 1 H-NMR(400MHz,CDCl 3 ):δ(ppm):2.15(s,12H,CH 3 ),2.30(s,6H,CH 3 ),6.96(s,4H,CHar),8.10(s,2H,CHar). 13 C-NMR(100MHz,CDCl 3 )δ(ppm):18.0,20.9,126.4,128.9,134.0,147.4,162.9。
2) Preparation of N, N' -bis (2, 4, 6-trimethylphenyl) decane-5, 6-diamine (10)
To a dry 100mL ampoule was added 2.92g (10.0 mmol) of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46 g/mol) and 50mL of tetrahydrofuran under nitrogen protection and dissolved with stirring. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction mixture was sufficiently cooled, 13.75mL (22.0 mmol) of a solution of butyllithium (1.6M in hexane) was slowly added dropwise via syringe. After the addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. During this process the solution gradually changed from cloudy to yellow and transparent. After the reaction, the reaction solution was cooled to 0 ℃ and 20mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, after separating the organic phase, the aqueous phase was further extracted with 20mL of ethyl acetate three times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off to give a yellow solid identified as N, N' -bis (2, 4, 6-trimethylphenyl) decane-5, 6-diamine (10) (CF: C) 28 H 44 N 2 (ii) a Mw 408.67 g/mol); weight 3.91g (9.57 mmol), yield: 97 percent. Calcd (found) for C 28 H 44 N 2 ；C,82.29(82.31)；H,10.85(11.01)；N,6.85(6.87). 1 H-NMR(600MHz,CDCl 3 ):δ(ppm):0.89(t,6H,3J(H,H)＝7.0Hz,CH 3 ),1.31(m,8H,CH 2 ),1.50(m,2H,CH 2 ),1.74(m,2H,CH 2 ),2.04(s,12H,CH 3 ),2.22(s,6H,CH 3 ),3.02(br,2H,NH),3.12(m,2H,CH),6.73(s,4H,CHar). 13 C-NMR(150MHz,CDCl 3 )δ(ppm):14.3,18.9,20.6,23.2,29.7,31.2,58.1,128.9,129.7,130.3,142.0。
3) Preparation of 4, 5-dibutyl-1, 3-bis (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-1)
4.32g (10.6 mmol) of N, N' -bis (2, 4, 6-trimethylphenyl) decane-5, 6-diamine (10) (Mw: 408.67 g/mol), 1.125g (10.73 mmol) of NH 4 BF 4 (Mw: 104.8431 g/mol) and 19mL CH (OEt) 3 The mixture was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oily phase was separated and 100mL of CH was used 2 Cl 2 Dissolving, filtering to remove insoluble substances to obtain clear solution, removing solvent by rotary evaporation, and vacuum drying to obtain brown viscous oil of 4, 5-dibutyl-1, 3-di (trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C) 29 H 43 BF 4 N 2 (ii) a Mw:506.48 g/mol). After passing through a celite column chromatography using dichloromethane as solvent, the solvent was removed by rotary evaporation and cooled for a long time to give 4.53g (8.94 mmol) of crystalline material in 84% yield. Calcd (found) for C 29 H 43 BF 4 N 2 ；C,68.77(68.62)；H,8.56(8.51)；N,5.53(5.32). 1 H NMR(600MHz,CDCl 3 )δ(ppm):8.33(s,1H,N-CH-N),6.94(s,4H,HMes),4.19(m bd,2H,CH-Bu),2.31(s,6H,CH 3 Mes),2.27(s,12H,CH 3 Mes),1.75(m,bd,4H,CH 2 -CH 2 ),1.26(m,bd 6H,CH 2 -CH 2 -),1.09(m,bd 2H,CH 2 -CH 2 -),0.81(t,6H,3J(H,H)＝7.27Hz,CH 2 -CH 3 ) 13 C NMR(150MHz,CDCl 3 )δ(ppm):158.2,140.5,135.7,134.7,130.5,129.0,69.5,33.0,27.1,22.4,21.9,21.0,18.4,18.1,13.7.
4) Preparation of 4, 5-dibutyl-1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride catalyst (I-1)
4.94g (9.75 mmol) of 4, 5-dibutyl-1, 3-di (trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C) were added to the dry flask under nitrogen protection 29 H 43 BF 4 N 2 (ii) a Mw:506.48 g/mol), 1.05g (9.34 mmol) of potassium tert-butoxide (Mw: 112.2 g/mol) and 50mL of dry tetrahydrofuran, and the resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.30 mmol) of Grubbs I (1) (Mw: 836.98 g/mol) as a ruthenium complex and 60mL of dry toluene, and the resulting mixture was heated to 70 ℃ and stirred for 4 hours. The solvent was removed by rotary evaporation, and the resulting solid material was subjected to silica gel column chromatography (petroleum ether/dichloromethane (1). Removing the solvent by vacuum rotary evaporation to obtain a viscous brownish red solid substance I-1 (Cf: C) 54 H 81 Cl 2 N 2 PRu, mw: 961.20). Weighing 3.97g (4.13 mmol); yield: 78 percent. Calcd (found) for C 54 H 81 Cl 2 N 2 PRu；C,67.48(67.41)；H,8.49(8.51)；N,2.91(2.95). 1 H NMR(600MHz,CDCl 3 ):δ0.70-2.81(m,51H),2.01(s,6H,CH 3 ),2.28(s,12H,CH 3 ),3.77(s,2H,NCHCHN),6.68-7.30(m,9H),19.39(s,1H,RuCHAr). 31 P-NMR(81.0MHz,CDCl 3 ):δ29.3.
Example 2: synthesis of hexyl-containing substituent catalyst 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (4, 5-dihexylimidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium (I-2)
The synthesis of the hexyl substituent-containing catalyst I-2 comprises the following steps:
1) Preparation of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9)
To a 500mL three-necked flask equipped with a dropping funnel, 3.73mL of an aqueous glyoxal (8) solution (40%) and 80mL of methanol were sequentially added, and the mixture was stirred to dissolve the glyoxal. To the dropping funnel was added 9.12mL of m-trimethylamine (7), 10mL of methanol, and slowly dropped into the flask. The reaction solution was stirred for 12 hours while controlling the temperature to about 22 ℃. In this process, a bright yellow precipitate slowly precipitated from the reaction solution. After the reaction is finished, filtering the reaction solution to obtain a yellow solid, washing the solid with water for three times, washing the solid with methanol for one time, and drying the solid in vacuum to obtain a yellow crystal product 9. Weighing 6.5g and yield 70%. Calcd (found) for C 20 H 24 N 2 C,82.15(82.12)；H,8.27(8.20). 1 H-NMR(400MHz,CDCl 3 ):δ(ppm):2.15(s,12H,CH 3 ),2.30(s,6H,CH 3 ),6.96(s,4H,CHar),8.10(s,2H,CHar). 13 C-NMR(100MHz,CDCl 3 )δ(ppm):18.0,20.9，126.4,128.9,134.0,147.4,162.9。
2) Preparation of N7, N8-bis (2, 4, 6-trimethyl) phenyltetradecane-7, 8-diamine (12)
To a dry 100mL ampoule was added 2.92g (0.01mol mw 292.46g/mol) of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9), 50mL of tetrahydrofuran under nitrogen and stirred to dissolve it. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction mixture was sufficiently cooled, 9.16mL (0.022 mol) of a hexyllithium (2.2M toluene solution) solution was slowly added dropwise by means of a syringe. After the dropwise addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. During this process the solution gradually changed from cloudy to yellow and transparent. After the reaction was completed, the reaction solution was cooled to 0 ℃,20 mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, after separating the organic phase, the aqueous phase was further extracted with 20mL of ethyl acetate three times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 4.32g (9.584 mmol, mw 450.76g/mol) of a yellow oily substance (12), yield: 96 percent. Calcd (found) for C 32 H 52 N 2 C,82.70(82.61)；H,11.28(11.41)；N,6.03(5.95). 1 H-NMR(400MHz,CDCl 3 ):δ(ppm):0.87(t,6H, 3 J(H,H)＝5.8Hz,CH 3 ),1.26(m,12H,CH 2 ),1.47(m,4H,CH 2 ),1.72(m,4H,CH 2 ),2.03(s,12H,CH 3 ),2.21(s,6H,CH 3 ),2.93(br,2H,NH),3.11(m,2H,CH),6.73(s,4H,CHar). 13 C-NMR(100MHz,CDCl 3 )δ(ppm):14.1,18.2,21.9,22.7,27.0,29.3,30.5,31.8,65.0,126.0,128.7,129.2,142.2。
3) Preparation of 4, 5-dihexyl-1, 3-bis (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-2)
4.32g (9.584 mmol) of N7, N8-bis (2, 4, 6-trimethyl) phenyltetradecane-7, 8-diamine (12) (Mw: 450.76 g/mol) (13), NH 4 BF 4 ( Mw:104.84g/mol;1.125g,10.73mmol,. About.10% molar excess) and 19mL CH (OEt) ) 3 The mixture was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oily layer was separated and 100mL CH was used 2 Cl 2 Dissolving, filtering to remove insoluble substances to obtain a clear solution, performing rotary evaporation to remove the solvent, performing vacuum drying to obtain a brown viscous oily substance which is 4, 5-dihexyl-1, 3-di (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-2), performing once diatomite column chromatography by using dichloromethane as a solvent, performing rotary evaporation to remove the solvent, and cooling for a long time to obtain 4.53g (8.05mmol, mw: 562.59 g/mol) of a crystalline substance with the yield of 75 percent. Calcd (found) for C 33 H 51 BF 4 N 2 ；C,70.45(70.52)；H,9.14(9.31)；N,4.98(5.02). 1 H NMR(400MHz,CO(CD 3 ) 2 )δ(ppm):8.45(s,1H,N-CH-N),6.99(s,4H,HMes),4.19(m bd,2H,CH-hexyl),2.35(s,12H,CH 3 Mes),2.32(s,6H,CH 3 Mes)，1.21-1.28(m,bd 20H,CH 2 -CH 2 -),0.85(t,6H, 3 J(H,H)＝5.9Hz,CH 2 -CH 3 ) 13 C NMR(100MHz,CO(CD 3 ) 2 )δ(ppm):144.2(N-C-N),140.3(CAr),135.6(CHAr),135.4(CHAr),129.7(CHAr),129.6(CHAr),129.4(CHAr),129.2(CAr),66.5(CH-hexyl),66.1(CH-Hexyl),28.3(CH 3 -Mes),17.8(CH 3 Mes),31.8(CH 2 ),29.3(CH 2 ),27.3(CH 2 ),25.6(CH 2 ),22.7(CH 2 ),14.1(CH 3 -hexyl)； 19 F NMR(376MHz,CO(CD 3 ) 2 )δ(ppm):-151.7.
4) Preparation of catalyst 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (4, 5-dihexylimidazolidinylidene) (benzylidene) (tricyclohexylphosphine) dichlororuthenium catalyst (I-2)
To a dry flask was added 4, 5-dihexyl-1, 3-bis (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-2) (Mw: 562.9g/mol;4.94g, 8.78mmol), potassium tert-butoxide (Mw: 112.2g/mol;1.05g, 9.33mmol) and 50mL of dry tetrahydrofuran under a nitrogen blanket. The resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.37mmol, mw 836.98g/mol) of ruthenium complex Grubbs I (1) and 60mL of dry toluene, and dissolved with stirring. The reaction mixture was heated to 70 ℃ and stirred for 2.5h while maintaining this temperature. And (3) after the reaction liquid is cooled to room temperature, performing silica gel column chromatography by using petroleum ether/dichloromethane (1). The solvent was removed by rotary evaporation in vacuo to give a viscous brownish red solid I-2,3.97g (0.39 mmol) (Cf: C) 58 H 89 Cl 2 N 2 PRu, mw 1017.3). Yield: 72.6 percent. 1 H NMR(400MHz,CDCl 3 ):δ0.88-2.44(m,59H),1.93(s,6H,CH 3 ),2.34(s,12H,CH 3 ),4.03(s,2H,NCHCHN),7.04-7.38(m,9H),19.16(s,1H,RuCHAr). 31 P-NMR(81.0MHz,CDCl 3 ):δ29.2.
Example 3: preparation of 4-butyl-5-hexyl-1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride (I-3)
1.1 Preparation of N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14)
To a dry 250mL ampoule was added 2.92g of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46g/mol;10.0 mmol), 100mL of tetrahydrofuran under nitrogen and dissolved with stirring. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction solution was sufficiently cooled, 4.17mL (10.0 mmol) of a solution of hexyllithium (2.4M in toluene) was slowly added dropwise via a syringe. The reaction solution was again cooled to-78 ℃ and 6.25mL (10.0 mmol) of butyllithium (1.6M in hexane) solution was slowly added dropwise via syringe. After the dropwise addition was complete, the reaction mixture was slowly warmed to room temperature with stirring and stirring was continued for 0.5h. Then, the reaction solution was cooled to 0 ℃ and 20mL of a saturated ammonium chloride solution was added to the reaction solution, followed by stirring for about 10 minutes. Standing until the solution is layered, separating out an organic phase, continuously extracting the aqueous phase with 20mL ethyl acetate for three times, combining the organic phases, and drying with anhydrous sodium sulfate. The solvent was removed by rotary evaporation to give an orange viscous oil which was identified as N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) 30 H 48 N 2 (ii) a Mw of 436.73 g/mol), a weight of 4.28g (9.80 mmol), and a yield of 98%.
1.2 Preparation of N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) by Grignard reagent
To a dry 250mL ampoule, 1.46g (5.0 mmol) of N-N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46 g/mol) and 100mL of tetrahydrofuran were added under nitrogen and dissolved with stirring. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred to cool. After the reaction mixture was sufficiently cooled, 7.5mL (6.0 mmol) of hexane was slowly added dropwise via syringeBased on magnesium bromide (0.8M, THF solution) solution. After the addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. During the process, the solution gradually changes from orange red to yellow and transparent. The reaction mixture was cooled to-78 deg.C and 3.75mL (6.0 mmol) of butyllithium (1.6M in hexane) solution was slowly added dropwise via syringe. After the dropwise addition was complete, the reaction mixture was slowly allowed to warm to room temperature with stirring and stirring was continued for 0.5h. The reaction solution is cooled to 0 ℃,20 mL of saturated ammonium chloride solution is added into the reaction solution, the solution is separated into layers, after an organic phase is separated, the aqueous phase is extracted for three times by using 20mL of ethyl acetate, and the organic phases are combined and dried by using anhydrous sodium sulfate. The solvent was distilled off to leave N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) as an orange viscous oil 30 H 48 N 2 (ii) a Mw of 436.73 g/mol), a weight of 2.13g (4.87 mol), and a yield of 97.4%.
2) Preparation of 4-butyl-5-hexyl-1, 3-bis (2, 4, 6-trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (II-3)
4.19g (9.58 mmol) of N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) 30 H 48 N 2 ；Mw:436.73g/mol)(13)、NH 4 BF 4 (Mw: 104.84g/mol;1.125g, 10.73mmol) and 19mL CH (OEt) 3 The mixture of (2) was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oil was separated and washed with 100mL CH 2 Cl 2 Dissolving, filtering to remove insoluble substances to obtain clear solution, removing solvent by rotary evaporation, and vacuum drying to obtain brown viscous oil which is 4-butyl-5-hexyl-1, 3-bis (2, 4,6 trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (15) (CF: C) 31 H 47 BF 4 N 2 (ii) a Mw 534.53 g/mol). Weighing 3.85g (7.20 mmol) and yield 75%. Performing primary chromatography with a diatomite column by using dichloromethane as a solvent, removing the solvent by rotary evaporation, and standing for a long time to obtain a crystalline substance.
3) Preparation of 4-butyl-5-hexyl-1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tricyclohexylphosphine) ruthenium dichloride (I-3)
4.69g (8.776 mmol) 4-butyl-5-hexyl-1, 3-bis (2, 4, 6-trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (15) (CF: C) were added to the dry flask under nitrogen protection 31 H 47 BF 4 N 2 (ii) a Mw 534.53 g/mol), 1.047g (9.33 mmol) of potassium tert-butoxide (Mw: 112.21 g/mol), 50mL of dry tetrahydrofuran, and the resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.37 mmol) of Grubbs I (Mw: 836.98 g/mol) as a ruthenium complex and 60mL of dry toluene, and the mixture was dissolved with stirring. The reaction mixture was heated to 70 ℃ and stirred for 2.5h while maintaining this temperature. And (3) after the reaction liquid is cooled to room temperature, performing silica gel column chromatography by using petroleum ether/dichloromethane (1). Removing solvent by vacuum rotary evaporation, and vacuum drying to obtain pink solid (I-3) (CF: C) 56 H 85 Cl 2 N 2 PRu; mw: 989.25), 3.82g (3.87 mmol), yield 72%.
With reference to the preparation methods of examples 1 and 2, the R substituent group obtained by the preparation was-C 10 H 21 (straight chain), -C 14 H 29 (straight chain), -C 18 H 37 (straight chain) and
the catalyst of (1).
Preparation of the catalyst composition:
a certain amount of the synthesized long alkyl chain modified catalyst is weighed, and liquid chlorinated paraffin is added to prepare a catalyst composition, and the catalyst composition can be stored for a long time at room temperature.
The chlorine content of the liquid chlorinated paraffin is as follows: 5% -65%;
the concentration ranges of the catalyst composition are: 0.08mol/L to 0.7mol/L;
the liquid chlorinated paraffin can be purchased or manufactured by self, and the self-manufacturing method refers to the following two methods: (1) Adding the measured liquid paraffin into a reaction kettle, introducing chlorine gas for reaction, washing with NaOH aqueous solution and aqueous solution in sequence until the acid value (mgkOH/g) is less than or equal to 0.3, decompressing and dehydrating until the water content is less than 2%, and discharging to obtain a finished product; (2) Adding metered liquid paraffin into a reaction kettle, dropwise adding thionyl chloride while stirring, refluxing for 5-7 h, and recovering excessive thionyl chloride under normal pressure. Washing with water and NaOH aqueous solution in sequence, reducing pressure and dehydrating until the water content is less than 2%, and discharging to obtain the finished product.
Examples of the preparation of the catalyst compositions are shown in table 1.
TABLE 1 preparation examples of catalyst compositions
Comparative example 1:
weighing 2.6g of commercial Grubbs 2 nd The catalyst was dissolved in 12.2mL of a paraffin solution having a chlorine content of 52% to prepare Grubbs 2 at a concentration of 0.25mol/L nd A catalyst solution. Commercial Grubbs 2 were found to be present at ambient temperatures below 10 deg.C nd The solubility of the catalyst in the chlorinated paraffin solution is reduced, the catalyst is easy to precipitate in the storage process, the catalytic activity is reduced, and the industrial application is not facilitated. Meanwhile, grubbs 2 which is commercialized nd The catalyst was dissolved in a paraffin solution having a chlorine content of 52% to prepare Grubbs 2 in a concentration of 0.05mol/L nd The catalyst solution was allowed to stand at room temperature for two weeks, and then more crystals were observed to precipitate. The experiment also shows that under normal temperature and pressure, the Grubbs 2 is commercialized nd The catalyst began to decompose after about 2 hours in toluene solvent, losing catalytic activity.
In addition, the catalyst with the R substituent group of methyl, ethyl or propyl is dissolved in the liquid chlorinated paraffin, so that the crystal of the catalyst is easily separated out in the long-time standing process, and the using effect is influenced.
Comparative example 2:
the present inventors attempted to commercialize Grubbs 2 nd The catalyst, the catalysts obtained in examples 1 and 2 of the present invention were dissolved in commercially available liquid paraffin, respectively. The results show that Grubbs 2 is commercially available nd The catalyst is insoluble in liquid paraffin; the catalysts prepared in examples 1 and 2 of the present invention were soluble in liquid paraffin, but the formed catalyst compositions were gel-like substances and were not transformed into liquid state even when heated to 60-70 ℃.
Comparative example 3:
the invention tries the chlorinated paraffin with different chlorine contents, when the chlorine content of the chlorinated paraffin is lower than 5 percent, the chlorinated paraffin is in a gel state, and needs a large amount of solvent to be diluted and dissolved before use, so the use is inconvenient. When the chlorine content is more than 65%, the liquid paraffin is in a high-viscosity state and even in a solid state (75% of commercial chlorinated paraffin is solid), which is not beneficial to the measurement of the catalyst, is difficult to be uniformly mixed with the substrate, causes local polymerization, and cannot complete the compression molding process.
Effect example 1
To evaluate the catalytic activity of the catalyst composition for ring-closing metathesis reactions, N-diallyl-4-methylbenzenesulfonamide (16) was selected as a substrate for testing.
Effect example 1.1:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.02mL of the catalyst composition prepared in example 4. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 219.7mg (0.984 mmol 11 H 13 NO 2 S; mw: 223.3), yield 98.4%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 1.2:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.006mL of the catalyst composition prepared in example 6. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction cooled to room temperature, the mixture was separated by column chromatography using petroleum ether/ethyl acetate (5) 11 H 13 NO 2 S; mw: 223.3), yield 98.8%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 1.3:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.008mL of the catalyst composition prepared in example 9. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 218.8mg (0.98mmol 11 H 13 NO 2 S; mw: 223.3), yield 98%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 1.4:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.007mL of the catalyst composition prepared in example 10. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) 11 H 13 NO 2 S; mw: 223.3), yield 98.1%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 2
To evaluate the catalytic activity of the catalyst composition for the cross-metathesis reaction between olefin molecules, allyl benzoate (18) and styrene (19) were selected as substrates and activity-tested.
Effect example 2.1:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19 and 0.083mL of the catalyst composition prepared in example 5. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 228.8mg (0.96mmol 16 H 14 O 2 Mw, 238.3), yield 96%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 2.2:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19 and 0.071mL of the catalyst composition prepared in example 6. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 229.2mg (0.962mmol 16 H 14 O 2 Mw: 238.3), yield 96.2%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH2)； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 2.3:
to a 5mL Schlenk bottle was added 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19, 0.25mL of the catalyst composition prepared in example 8. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 224.2mg (0.941mmol 16 H 14 O 2 Mw: 238.3), yield 94.1%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 2.4:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19 and 0.10mL of the catalyst composition prepared in example 9. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was then separated by column chromatography to give a cross-metathesis product 20 weighing 224.5mg (0.942mmol 16 H 14 O 2 Mw: 238.3), yield 94.2%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 3
To evaluate the use of the catalyst composition in ring-opening metathesis polymerization, dicyclopentadiene was selected as the monomer for testing.
Effect example 3.1:
200g of DCPD monomer was added dropwise to 0.6mL of the catalyst composition prepared in example 6, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 59.0MPa, tensile modulus 1919.2MPa and elongation at break 7.87%.
Effect example 3.2:
200g of DCPD monomer was added dropwise to 0.35mL of the catalyst composition prepared in example 7, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The results were: tensile strength 59.3MPa, tensile modulus 1919.7MPa and elongation at break 7.82%.
Effect example 3.3:
200g of DCPD monomer was added dropwise to 1.0mL of the catalyst composition prepared in example 9, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The results were: tensile strength 58.5MPa, tensile modulus 1911.6MPa and elongation at break 7.67%.
Effect example 3.4:
200g of DCPD monomer was added dropwise to 0.42mL of the catalyst composition prepared in example 11, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 80 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 58.9MPa, tensile modulus 1912.2MPa and elongation at break 7.61%.
Comparative example 3.1:
200g of DCPD monomer was weighed out, and 0.2g of Grubbs 2 dissolved in toluene solvent was added dropwise nd And mixing and stirring the catalyst uniformly, then carrying out defoaming treatment, and pouring a mold. And then setting a curing program of 60-100 ℃/2h for curing and forming to obtain a sample plate with the thickness of slightly less than 4mm (about 3.96 mm), wherein the surface of the plate has obvious flow mark phenomenon. This is mainly caused by the evaporation of the solvent toluene during the curing process. And finally, cutting a sample strip for mechanical property testing. The result is: high tensile strengthDegree 59.4MPa, tensile modulus 1913.4MPa and elongation at break 7.42%.
Comparative example 3.2:
for comparison experiments with the present invention, the present invention is strictly in accordance with the literature (Taber D.F., frankowski K.J., grubbs' catalyst in paraffin: an air-stable preparation for olefin catalysis [ J. ])]Grubbs 2 were prepared J.org.chem.,2003,68 (22): 6047-6048) nd A paraffin wax mixture of the catalyst. 200g of DCPD monomer is taken and added with 1.4g of Grubbs 2 nd A paraffin wax mixture of the catalyst (0.15 mmol/g,0.21 mmol) was found to be insoluble in DCPD monomer and was not homogeneously mixed even after stirring for 12 hours. And (3) raising the temperature to 40 ℃, and finding that polymerization occurs around the solid paraffin during stirring, so that the undissolved solid paraffin mixture is wrapped, and the solution cannot be defoamed and poured into a mold. The polymerization experiment fails, indicating that Grubbs 2 reported in the literature nd The paraffin wax mixture of the catalyst must be in the presence of a solvent to be catalytically effective.
Long term storage stability test
Storage stability verification experiments were performed after the catalyst compositions prepared in examples 4 to 11 were stored at room temperature for six months.
Effect example 4
After the catalyst was stored in chlorinated paraffin solution for 6 months, its catalytic activity for ring-closing metathesis was evaluated and tested using N, N-diallyl-4-methylbenzenesulfonamide (16) as a substrate.
Effect example 4.1:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.01mL of the catalyst composition prepared in example 4 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5The product 17, weighing 217.7mg (0.0975mmol 11 H 13 NO 2 S; mw: 223.3), yield 97.5%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 4.2:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.0057mL of the catalyst composition prepared in example 6 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) 11 H 13 NO 2 S; mw: 223.3), yield 97.8%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 4.3:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.008mL of the catalyst composition prepared in example 9 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, 217mg (0.972mmol 11 H 13 NO 2 S; mw: 223.3), yield 97.2%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 4.4:
to a 5mL single-neck flask, 251mg (1.0 mmol 13 H 17 NO 2 S; mw 251.1) substrate 16, 0.0067mL catalyst composition prepared in example 10 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) 11 H 13 NO 2 S; mw: 223.3), yield 97.5%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):2.42(s,3H),4.12(d, 3 J H-H ＝4.5Hz,4H),5.65(d, 3 J H-H ＝4.5Hz,2H),7.32(d, 3 J H-H ＝8.3Hz,2H),7.72(d, 3 J H-H ＝8.3Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。
Effect example 5
After the catalyst is stored in a chlorinated paraffin solution for 6 months, the catalytic activity of the catalyst on the olefin intermolecular cross-metathesis reaction is evaluated, and allyl benzoate (18) and styrene (19) are selected as substrates to be subjected to activity test.
Effect example 5.1:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19, and 0.083mL of the catalyst composition prepared in example 5 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. Cooling the reaction liquid to room temperature, and reacting the mixtureThe cross-metathesis product 20 was isolated by column chromatography, weighing 226.6mg (0.95mmol 16 H 14 O 2 Mw: 238.3), yield 95.1%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH2),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH2)； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 5.2:
to a 5mL Schlenk bottle was added 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19, and 3.61mL of the catalyst composition prepared in example 6 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to give a cross metathesis product 20 weighing 22.69mg (0.0952mmol 16 H 14 O 2 Mw: 238.3), yield 95.2%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1).
Effect example 5.3:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19, and 0.25mL of the catalyst composition prepared in example 8 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. When the reaction liquid is cooled to room temperature, the reaction is mixedThe compound was separated by column chromatography to give a cross metathesis product 20 weighing 222.8mg (0.935mmol 16 H 14 O 2 Mw: 238.3), yield 93.5%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 5.4:
to a 5mL Schlenk flask, 162mg (1.0 mmol 10 H 10 O 2 Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C 8 H 8 Mw 104.2) styrene 19, and 0.10mL of the catalyst composition prepared in example 9 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to give a cross metathesis product 20 weighing 223.3mg (0.937mmol 16 H 14 O 2 Mw, 238.3), yield 93.7%. 1 H NMR(400MHz,CDCl 3 ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH 2 ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH 2 )； 13 C-NMR(400MHz,CDCl 3 ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。
Effect example 6
After the catalyst is stored in the chlorinated paraffin solution for 6 months, the catalytic activity of the catalyst on the ring-opening metathesis polymerization reaction is evaluated, and dicyclopentadiene is selected as a monomer for testing.
Effect example 6.1:
200g of DCPD monomer was added dropwise to 0.6mL of the catalyst composition prepared in example 6 after storage for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.5MPa, tensile modulus 1905.3MPa, and elongation at break 8.11%.
Effect example 6.2:
200g of DCPD monomer are added dropwise to 0.35mL of the catalyst composition prepared in example 7 after storage for 6 months, and the mixture is stirred until the color becomes uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.9MPa, tensile modulus 1907.2MPa, and elongation at break 8.04%.
Effect example 6.3:
200g of DCPD monomer was added dropwise to 1.0mL of the catalyst composition prepared in example 9 stored for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength of 54.3MPa, tensile modulus of 1892.3MPa and elongation at break of 8.03%.
Effect example 6.4:
200g of DCPD monomer was added dropwise to 0.42mL of the catalyst composition prepared in example 11 stored for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 80 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.8MPa, modulus 1893.1MPa, and elongation at break 7.98%.
Effect example 7: preparation of Dicyclopentadiene/epoxy resin compositions
The information on the raw materials and reagents used in the following effect examples is as follows:
bisphenol a epoxy resin YN1828: purchased from Jiangsu Yangyang Hu chemical Co., ltd, and having an epoxy value of 0.51 to 0.54.
Dicyclopentadiene (2): DCPD.
4,4' -diaminodiphenyl sulfone: a DDS.
2,4, 6-tris (dimethylaminomethyl) phenol: DMP-30.
The formulations of the raw materials in effect examples 7.1 to 7.7 and comparative examples 7.1 to 7.4 are shown in tables 2 and 3, respectively.
Chlorinated paraffin:
the chlorine content is 5 percent, and the density is 0.82;
the chlorine content is 42 percent, and the density is 1.16;
the chlorine content is 52 percent, and the density is 1.24;
the chlorine content was 60% and the density was 1.45.
Mass calculation of the catalyst composition:
effect example (7.1-7.10) mass of catalyst = mass concentration of substance of catalyst composition catalyst molecular weight volume of catalyst composition in effect example
Mass of catalyst composition = mass of catalyst in effect examples (7.1 to 7.10) (% by volume of chlorinated paraffin whose chlorine content was determined in the respective examples)/mass of catalyst in the respective examples + mass of catalyst in effect examples (7.1 to 7.10)
TABLE 2
TABLE 3
Effect examples 7.1 to 7.7:
the preparation process of the dicyclopentadiene/epoxy resin composition is as follows:
(1) Mixing dicyclopentadiene and epoxy resin in advance to form a uniform solution;
(2) Adding a curing agent and a curing accelerator, and mechanically grinding by using a three-roll grinder;
(3) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, adding the catalyst composition, stirring and mixing the mixture firstly, and then mixing the mixture by using a three-roll grinder until the solution is uniform in color;
(4) And (4) placing the mixed solution obtained in the step (3) in a vacuum drying box to remove bubbles, and pouring and curing by adopting curing procedures of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h to obtain the thermosetting resin composition plate for the copper-clad plate.
Comparative example 7.1:
the preparation process of the epoxy resin of comparative example 7.1 is as follows:
(1) Adding 4,4' -diaminodiphenyl sulfone (DDS) curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol to epoxy resin, and mechanically grinding by using a three-roll grinder;
(2) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, the mixed solution is placed in a vacuum drying oven to remove bubbles, and the epoxy resin cured plate is obtained by adopting a curing procedure of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h for casting and curing.
Comparative example 7.2:
the process for preparing the polydicyclopentadiene resin of comparative example 7.2 is as follows:
(1) Adding a1, 3-bis (2, 4, 6-trimethylphenyl) -2- (4, 5-dibutylimidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium liquefaction catalyst into dicyclopentadiene, and stirring and mixing for 2min at normal temperature until the color is uniform;
(2) And (2) placing the mixed solution obtained in the step (1) in a vacuum drying oven to remove bubbles, and pouring and curing by adopting a curing program of 80 ℃/1h and 120 ℃/2h to obtain the polydicyclopentadiene resin cured product plate.
Comparative example 7.3:
the process for preparing the dicyclopentadiene/epoxy resin composition of comparative example 7.3 is as follows:
(1) Mixing dicyclopentadiene and epoxy resin in advance to form a uniform solution;
(2) Adding 4,4' -Diamino Diphenyl Sulfone (DDS) curing agent and 2,4, 6-tri (dimethylamino methyl) phenol, and mechanically grinding by using a three-roll grinder;
(3) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, the mixed solution is placed in a vacuum drying oven to remove bubbles, and the thermosetting resin composition plate for the copper-clad plate is obtained by adopting a curing procedure of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h for casting and curing.
Comparative example 7.4:
the process for preparing the dicyclopentadiene/epoxy resin composition of comparative example 7.4 is as follows:
(1) Mixing dicyclopentadiene and epoxy resin in advance to form a uniform solution;
(2) Adding 4,4' -Diamino Diphenyl Sulfone (DDS) curing agent and 2,4, 6-tri (dimethylamino methyl) phenol, and mechanically grinding by using a three-roll grinder;
(3) When the average particle size of solid particles in the mixed solution is less than 30 mu m, adding Grubbs secondary catalyst which is completely dissolved in toluene, firstly stirring and mixing, and then mixing by using a three-roll grinder until the solution is uniform in color;
(4) And (4) placing the mixed solution obtained in the step (3) in a vacuum drying box to remove bubbles, and pouring and curing by adopting curing procedures of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h to obtain the thermosetting resin composition plate for the copper-clad plate.
The dielectric properties of the sheets prepared in effect examples 7.1 to 7.7 and comparative examples 7.1 to 7.4 were tested, and the results are shown in Table 4,
TABLE 4
From the above table, the following points can be seen:
(1) Compared with the comparative example 7.1, the dielectric constant and the dielectric loss factor are obviously reduced along with the increase of the content of the dicyclopentadiene in the examples 7.1 to 5, which shows that the dielectric property of the epoxy resin can be improved by introducing the dicyclopentadiene nonpolar alicyclic chain structure.
(2) The significant increase in initial decomposition temperature (Td 5%) in example 7.3 compared to comparative example 7.3 indicates that the use of the dual cure system in the dicyclopentadiene/epoxy resin composite enables the two resins to each be fully cured and crosslinked to form an interpenetrating polymer network structure, thereby imparting good heat resistance thereto; (comparative example 7.3 No catalyst was added, dicyclopentadiene was present in the composition only as a monomer, and no crosslinking cure was performed).
(3) From example 7.3, example 7.6 and example 7.7, it can be seen that polydicyclopentadiene/epoxy resin composites having reduced dielectric properties can be prepared using different epoxy curing agents.
(4) Compared with the comparative example 7.4, the ruthenium carbene catalyst composition used in the examples 7.1 to 7.7 can fully cure the dicyclopentadiene, and the dicyclopentadiene and the epoxy resin are subjected to co-crosslinking, so that the compound with excellent performance is obtained.
Effect example 8: preparation of polydicyclopentadiene polymers
In effect examples 8 to 10, the actual amounts of the respective components in the liquid B = (sum of parts by weight of the liquid a)/[ (mass ratio of the liquid a to the liquid B) × (sum of parts by weight of the liquid B) ]
Effect example 8.1:
the formula of the catalyst composition prepared by the invention is the same as that of example 8, and the polydicyclopentadiene polymer is prepared by RIM reaction and injection molding of each component of the resin.
The weight parts of the raw materials of each component are as follows:
| dicyclopentaneDiene monomer | 99.95 parts of |
| Catalyst composition | 0.05 part |
| Comonomer (b): ethylene (CO) process | 10 portions of |
| Anti-aging agent: tinuvin B75 | 5 portions of |
The preparation process of the polydicyclopentadiene polymer comprises the following steps:
1. preparation of solution A: according to the formula design scheme, weighing dicyclopentadiene monomer to form solution A.
2. And (3) preparation of a liquid B: and weighing and mixing the catalyst composition, the comonomer and the anti-aging agent to form liquid B.
3. Leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use.
4. Injection molding: and (4) operating RIM glue injection equipment, mixing the A and B liquid materials on line, and injecting the mixture into a mold to complete reaction injection molding, thereby preparing the polydicyclopentadiene composite material.
5. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to finish the preparation of the polymer product.
And (3) the mass ratio of the solution A to the solution B is about 9, RIM equipment is adopted for reaction and injection molding, the injection speed is 500ml/min, the injection pressure is 6bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.
Effect example 8.2:
the formula of the catalyst composition prepared by the invention is the same as that of example 8, and the polydicyclopentadiene polymer is prepared by RIM reaction injection molding, and the formula of the resin system used by the polydicyclopentadiene polymer is the same as that of effect example 8.1. After the feed liquid A and the feed liquid B are uniformly mixed and respectively placed in a two-component storage tank of RIM equipment to be stored for 6 months under natural conditions, a composite material product is prepared by the RIM process, and the process parameters are the same as those of the example 1. The panels were cut out and the specific test results are shown in table 5.
Effect example 8.3:
the formula of the catalyst composition prepared by the invention is the same as that of the example 10, and the polydicyclopentadiene polymer is prepared by RIM reaction injection molding,
the weight parts of the raw materials of each component are as follows:
| dicyclopentadiene monomer | 80 portions |
| Catalyst composition | 20 portions of |
| Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 3 portions of |
| Functional filler: glass fiber | 5 portions of |
| Auxiliary agent: silane coupling agent A172 | 2 portions of |
| Auxiliary agent: toner powder | 2 portions of |
The preparation process of the polydicyclopentadiene polymer comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer and functional filler glass fiber to form solution A according to a formula design scheme, and stirring and mixing;
2. and (3) preparation of liquid B: weighing and mixing the catalyst composition, the comonomer and the auxiliary agent to form a solution B;
3. leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use;
4. injection molding: and (4) operating RIM glue injection equipment, mixing the A and B liquid materials on line, and injecting the mixture into a mold to complete reaction injection molding, thereby preparing the polydicyclopentadiene composite material.
5. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the composite material product.
And (3) the mass ratio of the solution A to the solution B is about 5, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 2L/min, the glue injection pressure is 15bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.
Effect example 8.4:
using the catalyst composition prepared in example 4, the components of the resin formulation were mixed uniformly and injection molded by RIM reaction to produce polydicyclopentadiene polymer.
The weight parts of the raw materials of each component are as follows:
| dicyclopentadiene monomer | 65 portions of |
| Catalyst composition | 35 portions of |
The preparation process of the polydicyclopentadiene polymer comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer according to a formula design scheme to form solution A.
2. And (3) preparation of liquid B: the catalyst composition was weighed and mixed to make solution B.
3. Leading in a material storage system: uniformly stirring to fully mix, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use.
4. Injection molding: and (3) operating RIM glue injection equipment, mixing the A and B liquid materials on line, injecting the mixture into a mold to complete reaction injection molding, and preparing the polydicyclopentadiene composite material.
5. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the polymer product.
And (3) the mass ratio of the solution A to the solution B is about 2, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 200ml/min, the glue injection pressure is 2bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.
Effect example 8.5:
the catalyst composition and the preparation process of the polydicyclopentadiene polymer are the same as those in the effect example 8.4; the difference is that the resin formula comprises the following raw materials in parts by weight, wherein a dicyclopentadiene monomer, a functional filler and an auxiliary agent are used as a solution A, a comonomer is mixed with a catalyst composition to form a solution B, and the mass ratio of the solution A to the solution B is about 3. The panels were cut out and the specific test results are shown in table 5.
Comparative example 8.1:
commercial Grubbs 2 nd The catalyst is dissolved in the toluene solutionTo obtain commercial Grubbs 2 nd Catalyst composition (mass ratio of Grubbs 2 commercialized) nd Catalyst: toluene =1:10 And injection molding by single-component RIM reaction to obtain the polydicyclopentadiene polymer.
The weight parts of the raw materials of each component are as follows:
| dicyclopentadiene monomer | 99.8 parts of |
| Commercial Grubbs 2nd catalyst composition | 0.2 part |
| Comonomer(s): 5-norbornene-2-carboxylic acid tert-butyl ester | 20 portions of |
| Functional filler: glass fiber | 5 portions of |
| Auxiliary agent: anti-aging agent Tinuvin B75 | 3 portions of |
During the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs 2 are added nd The catalyst composition, the comonomer, the auxiliary agent and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the glue injection speed is 200ml/min, the glue injection pressure is 20bar, the mold is insulated for 30min at 100 ℃ after the resin is filled, curing molding is carried out, and the test is finished after demolding and taking out. The panels were cut out and the specific test results are shown in table 5.
Comparative example 8.2:
the polydicyclopentadiene polymer is prepared by adopting a commercial tungsten-molybdenum metal carbene catalytic system and performing double-component RIM reaction injection molding.
The weight parts of the raw materials of the components are as follows:
| dicyclopentadiene monomer | 49.8 parts of |
| Main catalyst: molybdenum catalyst | 0.18 part |
| Dicyclopentadiene monomer | 50 portions of |
| Cocatalyst: aluminum diethyl monochloride | 0.02 portion |
The preparation process of the polydicyclopentadiene polymer comprises the following steps:
1. preparation of solution A: according to the formulation design scheme, 49.8 parts of dicyclopentadiene monomer and 0.18 part of molybdenum catalyst are weighed to form solution A.
2. And (3) preparation of liquid B: according to the formula design scheme, 50 parts of dicyclopentadiene monomer and 0.02 part of aluminum diethyl monochloride are weighed to form solution B.
3. Leading in a material storage system: uniformly stirring to fully mix, respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use
And the mass ratio of the solution A to the solution B is about 1, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 2L/min, the glue injection pressure is 3bar, the mold is subjected to heat preservation at 120 ℃ for 10min after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.
TABLE 5
Compared with the effect example 8.2, the effect example 8.1 shows that after the resin composition is stored for 6 months, the mechanical property of the prepared composite material has no obvious change, the effective period of the catalytic system is long, and the storage resistance is reliable.
Compared with the effect example 8.3, the effect example 8.1 shows that the composite material prepared by adding the glass fiber filler has higher strength compared with the composite material prepared by not adding the glass fiber filler, and can be used for reinforcing plastics.
Effect example 8.3 in comparison with comparative example 8.1, in comparison with commercial Grubbs 2 nd The composite material prepared by the catalyst has better mechanical property, and the composite material prepared by the effect example 8.3 has stable catalytic system and long storage period, and is more suitable for adding additional components such as functional filler and the like to improve the comprehensive performance of the product.
Compared with the comparative example 8.2, in the effect example 8.1, compared with a commercial tungsten-molybdenum metal carbene catalytic system, the mechanical property of the composite material prepared in the effect example 8.1 is remarkably improved.
Effect example 9: preparation of polydicyclopentadiene/epoxy resin composite material
Effect example 9.1:
using the catalyst composition obtained in example 7, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.
The liquid A comprises the following raw materials in parts by weight:
the liquid B comprises the following raw materials in parts by weight:
the preparation process of the epoxy/polydicyclopentadiene composite material comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer and bisphenol A epoxy resin to form A liquid according to a formula design scheme;
2. and (3) preparation of liquid B: weighing and mixing the catalyst composition, the epoxy resin curing agent and the curing accelerator to form a solution B;
3. mixing the additional components: uniformly mixing the functional filler, the comonomer and the auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;
4. leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use;
5. injection molding: and (3) operating RIM glue injection equipment, mixing the A and B liquid materials on line, injecting the mixture into a mold to complete reaction injection molding, and preparing the polydicyclopentadiene composite material.
6. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the composite material product.
And (3) reacting and injecting the solution A and the solution B by RIM equipment at a glue injection speed of 500ml/min and a glue injection pressure of 6bar, keeping the temperature of the mold at 80 ℃ after resin filling for 2h, curing and molding, demolding and taking a piece to finish the test, wherein the mass ratio of the solution A to the solution B is about 3. The panels were cut out and the specific test results are shown in Table 6.
Effect example 9.2:
the catalyst composition prepared in example 4 was used to prepare an epoxy/polydicyclopentadiene composite material by RIM reaction and injection molding.
The liquid A comprises the following raw materials in parts by weight:
the weight percentages of the raw materials of the components in the liquid B are as follows, the sum of the weight percentages of the catalyst composition, the curing agent and the curing accelerator is 100 percent, and the weight percentages of the other components are that the weight of each component accounts for the total weight of the catalyst composition, the curing agent and the curing accelerator:
the RIM forming process is the same as that of effect example 9.1. And (3) the mass ratio of the solution A to the solution B is about 3, RIM equipment is adopted for reaction and injection molding, the injection speed is 2L/min, the injection pressure is 15bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 6.
Effect example 9.3:
using the catalyst composition obtained in example 9, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 95 parts of |
| Bisphenol A epoxy resin | 5 portions of |
| Functional filler: carbon fiber powder | 5 portions of |
The liquid B comprises the following raw materials in parts by weight:
the RIM forming process is the same as that of effect example 9.1. And (3) the mass ratio of the solution A to the solution B is about 8, RIM equipment is adopted for reaction and injection molding, the injection speed is 5L/min, the injection pressure is 10bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 6.
Effect example 9.4:
using the catalyst composition obtained in example 8, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 80 portions |
| Bisphenol A epoxy resin | 20 portions of |
The liquid B comprises the following raw materials in parts by weight:
the RIM formation process was the same as in example 9.1. And (3) the mass ratio of the solution A to the solution B is about 15, RIM equipment is adopted for reaction and injection molding, the injection speed is 30L/min, the injection pressure is 25bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 6.
Comparative example 9.1:
commercial Grubbs 2 nd The catalyst was dissolved in toluene solution to produce commercial Grubbs 2 nd Catalyst composition (mass ratio of Grubbs 2 commercialized) nd Catalyst and toluene =1: 10), and the polydicyclopentadiene composite material is prepared by single-component RIM reaction and injection molding.
The weight parts of the raw materials of each component are as follows:
during the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs 2 are added nd The catalyst composition, the comonomer, the auxiliary agent and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the injection speed is 200mL/min, the injection pressure is 20bar, the mold is kept at 100 ℃ for 30min after the resin is filled, curing molding is carried out, and the mold is demoulded and taken to finish the test. The panels were cut out and the specific test results are shown in table 6.
Comparative example 9.2:
commercial Grubbs 2 nd The catalyst was dissolved in toluene solution to produce commercial Grubbs 2 nd Catalyst composition (mass ratio of Grubbs 2 commercialized) nd Catalyst: toluene =1:10 And injection molding by single-component RIM reaction to obtain the polydicyclopentadiene composite material.
The weight parts of the raw materials of the components are as follows:
| dicyclopentadiene monomer | 88.5 portions |
| Commercial Grubbs 2nd catalyst composition | 0.5 portion |
| Comonomer (b): norbornene based on carbon dioxide | 8 portions of |
| Functional filler: glass fiber | 3 portions of |
During the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs 2 are added nd The catalyst, the comonomer and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the glue injection speed is 2L/min, the glue injection pressure is 3bar, the mold is kept at 120 ℃ for 10min after resin filling, curing molding is carried out, and the test is finished after demolding and taking. The panels were cut out and the specific test results are shown in Table 6.
TABLE 6
| Serial number | Tensile Strength (MPa) | Tensile modulus (MPa) | Elongation at Break (%) |
| Effect example 9.1 | 65 | 5812 | 2.95 |
| Effect example 9.2 | 58 | 3156 | 4.85 |
| Effect example 9.3 | 62 | 4936 | 3.51 |
| Effect example 9.4 | 53 | 2074 | 3.97 |
| Comparative example 9.1 | 42 | 4527 | 3.15 |
| Comparative example 9.2 | 38 | 1692.1 | 8.41 |
Compared with the effect example 9.2, the effect example 9.1 shows that the strength and the elastic modulus of the product are obviously improved and the reinforcing effect of the fiber is obvious when the glass fiber functional filler is added into the complex system.
Effect example 9.1 in comparison with comparative example 9.1, it can be seen that the formulated system is comparable to commercial Grubbs 2 nd The composite material prepared by the catalyst has higher strength.
Compared with the comparative example 9.2, in the effect example 9.2, compared with the commercial polydicyclopentadiene product, the mechanical property of the composite material prepared in the effect example 9.2 is obviously improved, and especially the deformation resistance of the product is obviously improved due to the increase of the elastic modulus.
Effect example 9.3 demonstrates that the addition of carbon fiber can significantly improve the elastic modulus and strength of the material.
Effect example 9.4 in comparison with effect example 9.1 and comparative example 9.1, it is understood that the addition of the epoxy resin system can improve the strength and deformation resistance of the polydicyclopentadiene resin system to some extent.
Effect example 10: preparation of polydicyclopentadiene/epoxy resin-based fiber-reinforced composite material
In effect example 10, the actual amount of the fiber reinforcement = (the amount of the fiber reinforcement in parts by weight) = (the sum of the amounts of the liquid a and the liquid B in parts by weight)
Effect example 10.1:
the catalyst composition prepared in example 5 is used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin based composite material by an RTM process.
The liquid A comprises the following raw materials in parts by weight:
the liquid B comprises the following raw materials in parts by weight:
| catalyst composition | 0.33 |
| Epoxy curing agent: methyl tetrahydrophthalic anhydride | 97.79 portions |
| Epoxy curing accelerator: 2-methylimidazole | 1.88 parts |
| Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 15 portions of |
| Auxiliary agent: polymerization regulator triphenyl phosphine | 0.6 part |
The preparation process of the polydicyclopentadiene/epoxy resin system comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer and bisphenol A epoxy resin to form A liquid according to a formula design scheme;
2. and (3) preparation of liquid B: weighing and mixing a liquefaction catalyst, an epoxy resin curing agent and a curing accelerator to form a liquid B;
3. mixing the additional components: uniformly mixing the functional filler, the comonomer and the auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;
4. the molding process comprises the following steps: uniformly stirring to fully mix all the components, and mixing the solution A and the solution B to prepare a polydicyclopentadiene/epoxy resin system.
The mass ratio of the solution A to the solution B is about 10: and 7, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
And (3) preparing the fiber reinforced resin matrix composite material with the fiber mass fraction of 50% by taking continuous glass fibers as a reinforcement. The preparation process of the composite material comprises the following steps:
1. treating the die: the RTM mould is cleaned, and a hole sealing agent and a release agent can be coated to facilitate demoulding and improve the apparent effect of a product;
2. preparation of continuous glass fiber reinforcement: finishing continuous glass fiber cutting, laying and reinforcement shaping according to product design requirements, trimming and then placing in an RTM mold cavity; wherein the mass of the continuous glass fiber accounts for 50% of the mass of the composite material;
3. mold closing and glue injection: closing the mold to ensure good sealing, injecting the prepared epoxy/polydicyclopentadiene resin glue solution into the mold cavity by using an RTM glue injection machine, heating for curing, demolding and taking out the parts to finish the preparation of the composite material.
The continuous glass fiber twill used in this example had an areal density of 250g/m 2 The design thickness of the board is 2mm, the warp direction of the fabric is marked as 0 degree direction, and the ply design of the composite board is [0/90 ]] 5 There are 10 layers of balanced symmetrical ply. Fiber reinforcement preparation is accomplished with reference to this material and ply design. The glue injection pressure in the RTM process forming process of the composite material is 6bar, and the system curing system is 80 ℃ for 5h. The panels were cut out and the specific test results are shown in Table 7.
Effect example 10.2:
the catalyst composition prepared in example 9 was used to prepare a carbon fiber-reinforced polydicyclopentadiene/epoxy resin composite material by an RTM process.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 40 portions of |
| Bisphenol A epoxy resin | 60 portions of |
| Functional filler: silicon dioxide | 10 portions of |
The liquid B comprises the following raw materials in parts by weight:
| catalyst composition | 1.05 parts |
| Epoxy curing agent: methylhexahydrophthalic anhydride | 94.21 parts of |
| Epoxy curing accelerator: DMP-30 | 4.74 parts of |
| Comonomer(s): 5-norbornene-2-carboxylic acid tert-butyl ester | 10 portions of |
| Auxiliary agent: anti-aging agent (Tinuvin 571) | 0.98 portion of |
The process for preparing polydicyclopentadiene/epoxy resin system was the same as in effect example 10.1. The mass ratio of the solution A to the solution B is about 5: 3, and the solution A and the solution B are uniformly mixed by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
The preparation process of the carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of effect example 10.1. The difference is that the fiber reinforcement in the effect example is continuous carbon fiber, and the area density of the unidirectional fabric is 160g/m 2 The design thickness of the board is 1mm, the direction of the unidirectional fabric along the fiber direction is marked as 0 degree, and the ply design of the composite board is [0/90/0 ]] 3 And 9 layers are uniformly and symmetrically layered. Fiber reinforcement preparation is accomplished with reference to this material and ply design. In the embodiment, the mass of the continuous carbon fiber accounts for 40% of the mass of the composite material; glue injection pressure in composite material RTM process forming processThe force is 3bar, and the curing system is 120 ℃/2h. The panels were cut out and the specific test results are shown in Table 7.
Effect example 10.3:
the catalyst composition prepared in example 6 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material by a vacuum flow guiding process.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 50 portions of |
| Bisphenol A epoxy resin | 50 portions of |
| Auxiliary agent: coupling agent KH560 | 0.65 part of |
| Auxiliary agent: anti-aging agent (2, 6-di-tert-butyl-4-methylphenol) | 1.14 parts of |
The liquid B comprises the following raw materials in parts by weight:
| catalyst composition | 1.13 parts of |
| Epoxy curing agent: methyl-5-noriceLamene-2, 3-dicarboxylic anhydrides | 94.39 parts of |
| Epoxy curing accelerator: DMP-30 | 4.49 parts |
| Comonomer(s): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 5 portions of |
The process for preparing polydicyclopentadiene/epoxy resin system is the same as in effect example 10.1. The mass ratio of the solution A to the solution B is about 2:1, and the solution A and the solution B are uniformly mixed by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
And (3) preparing the fiber reinforced resin matrix composite material with the mass fraction of the fiber of 60 percent by taking the continuous glass fiber as a reinforcement. The preparation process of the composite material comprises the following steps:
1. preparing a prefabricated body: according to the design scheme of the laying layer, finishing cutting, laying layer shaping and trimming of the fiber fabric for later use;
2. bag making: preparing a vacuum bag used in the vacuum diversion molding process, and detecting good air tightness;
3. injecting glue: under the action of vacuum negative pressure, the resin glue solution is poured;
4. curing and forming: and heating the preformed blank after glue injection to solidify the preformed blank, and demoulding to take the part.
In this effect example, the type of continuous glass fiber used and the ply design are the same as in effect example 10.1. In the vacuum diversion process, the vacuum degree of the vacuum bag is generally more than 920mbar; during air tightness detection, the requirement that the pressure drop is less than 50mbar within 5min is met, and the curing system of the product is 120 ℃/2h. The panels were cut out and the specific test results are shown in Table 7.
Effect example 10.4:
the catalyst composition prepared in example 5 is used for preparing a continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum diversion process.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 60 portions of |
| Bisphenol A epoxy resin | 40 portions of |
| Functional filler: graphite powder | 5 portions of |
| Auxiliary agent: polymerization regulator triethyl phosphite | 0.02 portion |
| Auxiliary agent: coupling agent KH560 | 0.65 part of |
The liquid B comprises the following raw materials in parts by weight:
| catalyst composition | 1.85 parts of |
| Epoxy curing agent: methylhexahydrophthalic anhydride | 60.83 portions |
| Epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride | 35.58 parts |
| Epoxy curing accelerator: 2-Ethylimidazole | 1.73 parts of |
| Comonomer(s): 5-norbornene-2-carboxylic acid tert-butyl ester | 5 portions of |
The preparation process of polydicyclopentadiene/epoxy resin system is the same as that of effect example 10.1. The mass ratio of the solution A to the solution B is about 5:2, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
The preparation process of the continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of the effect example 10.3. The difference is that the fiber reinforcement described in the effect example is continuous carbon fiber, and the area density of the unidirectional fabric is 160g/m 2 The design thickness of the board is 1mm, the direction of the unidirectional fabric along the fiber direction is marked as 0 degree, and the ply design of the composite board is [0/90/0 ]] 3 And 9 layers are uniformly and symmetrically layered. And finishing the preparation of the fiber reinforcement body according to the material and the layering design scheme. In the embodiment, the mass of the continuous carbon fiber accounts for 70% of the mass of the composite material; the results of the composite material testing are shown in Table 7.
Effect example 10.5:
using the catalyst composition prepared in example 10, a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite was prepared by a wet molding process.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 80 portions of |
| Bisphenol A epoxy resin | 20 portions of |
| Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 5 portions of |
| Comonomer (b): 5-norbornene-2-carboxylic acid tert-butyl ester | 5 portions of |
| Functional filler: graphite powder | 5 portions of |
The liquid B comprises the following raw materials in parts by weight:
the preparation process of polydicyclopentadiene/epoxy resin system is the same as that of effect example 10.1. The mass ratio of the solution A to the solution B is about 5:2, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
And (3) preparing the fiber reinforced resin matrix composite material with the mass fraction of the fiber of 75 percent by taking the continuous glass fiber as a reinforcement. The composite material is prepared by adopting a wet-process die pressing process, and the forming process comprises the following steps:
1. preparing a prefabricated body: according to the design scheme of the laying layer, finishing cutting, laying layer shaping and trimming of the fiber fabric for later use;
2. resin coating: uniformly coating the resin glue solution on the prefabricated body in the die cavity;
3. die assembly and press forming: and (3) closing the mold by a press, controlling the pressing process, heating, curing and molding, and demolding and taking out the workpiece.
In this effect example, the type of continuous glass fiber used and the ply design are the same as in effect example 10.1. The prepressing pressure in the wet-method mould pressing process is 0.2MPa, the pressing pressure is 1.5MPa, and the curing system of a resin system is 120 ℃/20min; the panels were cut out and the specific test results are shown in Table 7.
Effect example 10.6:
the catalyst composition prepared in the embodiment 6 is adopted to prepare the continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum diversion process, and the formula of the resin system used by the composite material is the same as that of the effect example 10.3.
And mixing the solution A and the solution B and the accessory components, storing the mixture at room temperature for 6 months, and preparing a composite material product by adopting a vacuum diversion process, wherein the process parameters are the same as those of the effect example 10.3. The panels were cut out and the specific test results are shown in Table 7.
Comparative example 10.1:
using the catalyst composition obtained in example 6, a polydicyclopentadiene/epoxy resin composite material was obtained by a RIM process.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 50 portions of |
| Bisphenol A epoxy resin | 50 portions of |
The liquid B comprises the following raw materials in parts by weight:
| catalyst composition | 1.13 parts of |
| Epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride | 94.39 parts |
| Epoxy curing accelerator: DMP-30 | 4.49 parts |
| Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 5 portions of |
| Auxiliary agent: coupling agent KH560 | 0.65 portion |
| Auxiliary agent: anti-aging agent (2, 6-di-tert-butyl-4-methylphenol) | 1.14 parts |
The preparation process of the polydicyclopentadiene/epoxy resin composite material comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer, functional filler and auxiliary agent according to a formula design scheme to form solution A;
2. and (3) preparation of a liquid B: weighing and mixing a liquefaction catalyst and a comonomer to form a solution B;
3. mixing the additional components: uniformly mixing a comonomer and an auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;
4. leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use;
5. injection molding: and (3) operating RIM glue injection equipment, mixing the A and B liquid materials on line, injecting the mixture into a mold to complete reaction injection molding, and preparing the polydicyclopentadiene composite material.
6. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the composite material product.
And (3) the mass ratio of the solution A to the solution B is about 2, RIM equipment is adopted for reaction and injection molding, the injection speed is 1500ml/min, the injection pressure is 6bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 7.
Comparative example 10.2:
using the catalyst composition prepared in example 6, polydicyclopentadiene material was prepared by RIM reaction injection molding.
The weight parts of the raw materials of each component are as follows:
| dicyclopentadiene monomer | 99.7 parts of |
| Catalyst composition | 0.3 part |
| Comonomer(s): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 15 portions of |
| Functional filler: graphite powder | 5 portions of |
| Auxiliary agent: polymerization regulator triphenyl phosphine | 3.2 parts of |
The resin system and the RIM forming process method of the composite material are the same as the comparative example 10.1; the difference is that the solution a in the present embodiment only contains dicyclopentadiene monomer, and the mass ratio of the dicyclopentadiene monomer to the solution B is about 5. The specific test results are shown in table 7.
Comparative example 10.3:
the catalyst composition prepared in the embodiment 6 of the invention is used for preparing the continuous glass fiber reinforced polydicyclopentadiene by the RTM process, and the formula of the resin system used by the catalyst composition is the same as that of the comparative example 10.2. The RTM process is adopted to prepare the composite material product, and the forming method and the process parameters are the same as those in the effect example 10.1. The panels were cut out and the specific test results are shown in Table 7.
Comparative example 10.4:
the existing commercial ruthenium carbene olefin metathesis catalyst can only be stored for a long time under the condition of low temperature and solid state. When in use, the catalyst can only be dissolved in a common solvent to prepare a solution with a certain concentration, and the catalyst in the solution state is easy to decompose, so that the catalyst is deactivated. Therefore, ruthenium carbene olefin metathesis catalysts have only been currently formulated in olefin polymerization processes.
A commercial ruthenium carbene catalytic system is adopted, and a vacuum flow guide process is carried out to prepare the continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material.
The liquid A comprises the following raw materials in parts by weight:
| dicyclopentadiene monomer | 50 portions of |
| Bisphenol A epoxy resin | 50 portions of |
The liquid B comprises the following raw materials in parts by weight:
| epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride | 95.46 parts |
| Epoxy curing accelerator DMP-30 | 4.54 parts of |
| Comonomer(s): methyl-5-norbornene-2, 3-dicarboxylic anhydride | 5 portions of |
| Auxiliary agent: coupling agent KH560 | 0.65 portion |
| Auxiliary agent: anti-aging agent (2, 6-di-tert-butyl-4-methylphenol) | 1.14 parts |
The liquid C comprises the following raw materials in parts by weight:
the preparation process of the polydicyclopentadiene/epoxy resin system comprises the following steps:
1. preparation of solution A: weighing dicyclopentadiene monomer and bisphenol A epoxy resin to form A liquid according to a formula design scheme;
2. and (3) preparation of a liquid B: weighing and mixing an epoxy resin curing agent and a curing accelerator to form a solution B;
3. mixing the additional components: uniformly mixing the functional filler, the comonomer and the auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;
4. and C, preparation of a solution C: mixing Grubbs 2 nd The catalyst is fully dissolved in the toluene solution to form a solution C.
5. The molding process comprises the following steps: and mixing the solution A and the solution B, adding the solution C, and uniformly mixing to obtain the resin system for the composite material.
The mass ratio of the liquid A, the liquid B and the liquid C is about 200: 100:1, the liquid A, the liquid B and the liquid C are uniformly mixed by adopting a mechanical stirring mode, the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.
And (3) preparing the fiber reinforced resin matrix composite material with the fiber mass fraction of 60% by taking continuous glass fiber as a reinforcement. The preparation process of the composite material is the same as that of effect example 10.3. The specific test results are shown in table 7.
TABLE 7
| Serial number | Tensile strength | Modulus of elasticity | Elongation at break |
| Effect example 10.1 | 557MPa | 48GPa | 3.41％ |
| Effect example 10.2 | 1865MPa | 75GPa | 2.74％ |
| Effect example 10.3 | 712MPa | 57GPa | 3.06％ |
| Effect example 10.4 | 2184MPa | 136GPa | 1.89％ |
| Effect example 10.5 | 852MPa | 64GPa | 2.83％ |
| Effect example 10.6 | 703MPa | 53GPa | 3.31％ |
| Comparative example 10.1 | 63MPa | 2917MPa | 4.42％ |
| Comparative example 10.2 | 48MPa | 2162MPa | 5.71％ |
| Comparative example 10.3 | 469MPa | 36GPa | 4.2％ |
| Comparative example 10.4 | 708MPa | 55GPa | 3.05％ |
Claims (24)
1.A composition, characterized in that it comprises, in parts by weight: 60-100 parts of dicyclopentadiene and 0.01-35 parts of catalyst composition;
the catalyst composition comprises a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5-65%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin;
wherein R is 1 And R 2 Independently is C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 An alkyl group;
R 1-1 independently is C 6 -C 10 And (4) an aryl group.
2. The composition of claim 1,
the chlorine content of the chlorinated paraffin is 5-60%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin;
and/or the mass concentration of the ruthenium carbene compound shown as the formula I or the salt thereof in the chlorinated paraffin is 0.08-0.7 mol/L;
and/or, said C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl is independently C 4 -C 10 An alkyl group;
and/or said is R 1-1 Substituted C 4 -C 18 In the alkyl radical, R 1-1 The number of (b) is 1, 2 or 3, and when 2 or 3, they are the same or different;
and/or, said C 6 -C 10 Aryl is phenyl or naphthyl;
and/or, R 1 And R 2 The same or different;
and/or the purity of the dicyclopentadiene is more than or equal to 90 percent;
and/or, the dosage of the dicyclopentadiene is 65-99.95 parts by weight;
and/or, the dosage of the catalyst composition is 0.03-33 parts by weight;
and/or, the composition further comprises one or more of a comonomer, a functional filler and an auxiliary agent.
3. The composition of claim 2,
the chlorine content of the chlorinated paraffin is 5%, 42%, 52% or 60%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin;
and/or the mass concentration of the ruthenium carbene compound shown as the formula I or the salt thereof in the chlorinated paraffin is 0.1-0.6 mol/L;
and/or, said C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl is independently C 4 -C 6 An alkyl group;
and/or the purity of the dicyclopentadiene is more than or equal to 98 percent;
and/or, the amount of dicyclopentadiene is 65 parts, 75 parts, 90 parts or 99.95 parts by weight;
and/or, the catalyst composition is used in an amount of 0.04 parts, 12.59 parts, 13.64 parts or 32.5 parts by weight;
and/or, when the composition further comprises a comonomer, the comonomer is one or more of norbornene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene, propylene, isoprene, styrene, butadiene, methyl-5-norbornene-2, 3-dicarboxylic anhydride, tert-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-carbaldehyde, and 5-norbornene-2-methanol;
and/or, when the composition further comprises a comonomer, the amount of the comonomer is 1-20 parts;
and/or, when the composition further comprises a functional filler, the functional filler is one or more of graphite powder, mica powder, montmorillonite, titanium dioxide, silica, glass fiber, basalt fiber, carbon fiber, polyethylene fiber and aramid fiber;
and/or, when the composition further comprises a functional filler, the amount of the functional filler is 3-20 parts;
and/or, when the composition further comprises an auxiliary agent, the auxiliary agent is one or more of a polymerization regulator, an anti-aging agent, a coupling agent, a toner, a heat stabilizer, a flame retardant and a mold release agent.
4. The composition of claim 3,
said C 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl is independently C 4 Alkyl radical, C 5 Alkyl or C 6 An alkyl group.
5. The composition of claim 4, wherein C is 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl is independently n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl.
6. The composition of claim 5, wherein C is 4 -C 18 Alkyl or by R 1-1 Substituted C 4 -C 18 C in alkyl 4 -C 18 Alkyl is independently n-butyl or n-hexyl.
7. The composition according to any one of claims 3 to 6,
the mass concentration of the ruthenium carbene compound shown as the formula I or the salt thereof in the chlorinated paraffin is 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.55mol/L or 0.6mol/L;
and/or the ruthenium carbene compound shown in the formula I is in any structure,
and/or, when the composition further comprises a comonomer, the comonomer is one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and tert-butyl 5-norbornene-2-carboxylate;
and/or, when the composition further comprises a comonomer, the comonomer is used in an amount of 1 to 17 parts;
and/or, when the composition further comprises a functional filler, the functional filler is glass fiber and/or graphite powder;
and/or, when the composition further comprises a functional filler, the functional filler is used in an amount of 3-7 parts;
and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a polymerization regulator, and the polymerization regulator is one or more of triphenyl phosphorus, triethyl phosphite, tributyl phosphite, ethylene glycol dimethyl ether, benzophenone and isopropyl ether;
and/or, when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises a polymerization regulator, the dosage of the polymerization regulator is 7-13 parts by weight;
and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, tinuvin 571, tinuvin 765, tinuvin B75, tinuvin B88, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531 and UV-770;
and/or, when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises an anti-aging agent, the dosage of the anti-aging agent is 1-5 parts by weight;
and/or, when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises a coupling agent, the coupling agent is a silane coupling agent;
and/or, when the composition further comprises an auxiliary agent, the amount of the coupling agent is 1-3 parts by weight when the auxiliary agent comprises the coupling agent;
and/or when the composition further comprises an auxiliary agent, the auxiliary agent comprises a toner, and the amount of the toner is 1-3 parts by weight.
8. The composition of claim 7,
when the composition further includes a comonomer, the comonomer is used in an amount of 1.89 parts, 7.38 parts, or 16.36 parts;
and/or, when the composition further comprises a functional filler, the amount of the functional filler is 5 parts;
and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a polymerization regulator, the polymerization regulator is triphenyl phosphorus and/or triethyl phosphite;
and/or, when the composition further comprises an auxiliary agent, and the auxiliary agent comprises a polymerization regulator, the dosage of the polymerization regulator is 10 parts by weight;
and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone;
and/or when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises an anti-aging agent, the anti-aging agent is used in an amount of 3.69 parts by weight;
and/or, when the composition further comprises an auxiliary agent, and the auxiliary agent comprises a coupling agent, the coupling agent is a silane coupling agent A172;
and/or, when the composition further comprises an auxiliary agent, the amount of the coupling agent is 1.26 parts by weight when the auxiliary agent comprises the coupling agent;
and/or when the composition further comprises an auxiliary agent, the auxiliary agent comprises a toner, and the amount of the toner is 1.26 parts by weight.
9. The composition according to any one of claims 1 to 6,
the catalyst composition consists of a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin;
and/or, the composition is any one of the following combinations:
combination C1: dicyclopentadiene and a catalyst composition;
combination C2: dicyclopentadiene, catalyst composition and comonomer;
combination C3: dicyclopentadiene, catalyst compositions, comonomers and age resisters;
combination C4: dicyclopentadiene, catalyst compositions, comonomers, functional fillers and polymerization regulators;
a combination C5: dicyclopentadiene, a catalyst composition, a comonomer, a functional filler, a coupling agent and a toner.
10. The composition of claim 9, wherein the catalyst composition is any combination of:
combination A1:
and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 5%, 42%, 52% or 60%;
combination A2:
and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 5%, 42%, 52% or 60%;
combination A3:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%;
combination A4:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 42%;
combination A5:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%;
combination A6:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 60%; />
Combination A7:
and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%;
combination B1:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination B2:
and chlorinated paraffin having a chlorine content of 42%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;
combination B3:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.35mol/L;
combination B4:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin was 0.6mol/L;
combination B5:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L; />
Combination B6:
and chlorinated paraffin having a chlorine content of 42%>
The amount concentration of the substance in the chlorinated paraffin was 0.25mol/L;
combination B7:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;
combination B8:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin was 0.6mol/L;
combination B9:
and chlorinated paraffin having a chlorine content of 52%>
The mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;
combination B10:
and a chlorine content of 42%Chlorinated paraffin>
The mass concentration of the substance in the chlorinated paraffin was 0.35mol/L;
combination B11:
and chlorinated paraffin having a chlorine content of 5%>
The mass concentration in the chlorinated paraffin was 0.55mol/L; />
Combination B12:
and chlorinated paraffin having a chlorine content of 60%>
The mass concentration of the substance in the chlorinated paraffin is 0.2mol/L;
combination B13:
and chlorinated paraffin having a chlorine content of 52%,
the amount concentration of the substance in the chlorinated paraffin was 0.35mol/L.
11. The composition of claim 9, wherein the composition is any one of the following in combination:
combination D1: 65-99.95 parts of dicyclopentadiene and 0.03-33 parts of catalyst composition;
combination D2: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer and 1-5 parts of anti-aging agent;
combination D3: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler and 7-13 parts of polymerization regulator;
combination D4: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler, 1-3 parts of coupling agent and 1-3 parts of toner;
combination D5: 65-99.95 parts of dicyclopentadiene and 0.03-33 parts of catalyst composition; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%;
combination D6: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer and 1-5 parts of age resister; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; the comonomer is one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and 5-norbornene-2-carboxylic acid tert-butyl ester; the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone;
combination D7: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler and 7-13 parts of polymerization regulator; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; the comonomer is one or more of ethylene, methyl-5-norbornene-2, 3-dicarboxylic anhydride and 5-norbornene-2-carboxylic acid tert-butyl ester; the functional filler is glass fiber and/or graphite powder; the polymerization regulator is triphenyl phosphorus and/or triethyl phosphite;
combination D8: 65-99.95 parts of dicyclopentadiene, 0.03-33 parts of catalyst composition, 1-17 parts of comonomer, 3-7 parts of functional filler, 1-3 parts of coupling agent and 1-3 parts of toner; saidThe catalyst composition is
And chlorinated paraffin with a chlorine content of 52%; the functional filler is glass fiber and/or graphite powder; the coupling agent is a silane coupling agent A172;
combination D9: 65 parts of dicyclopentadiene and 32.5 parts of catalyst composition; the catalyst composition is
And chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D10: 99.95 parts of dicyclopentadiene, 0.04 part of catalyst composition, 7.38 parts of ethylene and 753.69 parts of Tinuvin B; the catalyst composition is
And chlorinated paraffin having a chlorine content of 5%>
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D11: 75 parts of dicyclopentadiene, 13.64 parts of catalyst composition, 16.36 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 5 parts of graphite powder and 10 parts of triphenyl phosphorus; the catalyst composition is
And chlorinated paraffin with a chlorine content of 5%; />
The mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;
combination D12: 80 parts of dicyclopentadiene and a catalyst12.59 parts of composition, 1.89 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 5 parts of glass fiber, 1.26 parts of silane coupling agent A and 1.26 parts of toner; the catalyst composition is
And chlorinated paraffin having a chlorine content of 52%>
The amount concentration of the substance in the chlorinated paraffin was 0.3mol/L.
12. The composition of claim 1,
R 1 and R 2 Independently is C 4 -C 18 An alkyl group.
13. The composition of claim 12,
R 1 and R 2 Independently n-butyl or n-hexyl.
14. A resin material prepared from the composition of any one of claims 1 to 13 as a starting material.
15. A preparation method of a resin material is characterized by comprising the following steps: the resin material is prepared by taking the composition as defined in any one of claims 1-13 as a raw material, uniformly mixing dicyclopentadiene and the catalyst composition, and curing and molding the mixture.
16. The method of claim 15, wherein the method uses a RIM process.
17. The method of claim 16, wherein the RIM process comprises the steps of:
(1) Taking dicyclopentadiene as liquid A;
(2) Taking the catalyst composition as a liquid B;
(3) Introducing the solution A and the solution B into a material storage system for later use;
(4) The solution A and the solution B are subjected to reaction injection molding in RIM equipment;
(5) And curing to obtain the resin material.
18. A preparation method of a resin material is characterized by comprising the following steps: the resin material is prepared by taking the composition as defined in any one of claims 1-13 as a raw material, uniformly mixing dicyclopentadiene and the catalyst composition, adding one or more of a comonomer, a functional filler and an auxiliary agent, and curing and molding.
19. The method of claim 18, wherein the method uses a RIM process.
20. The method of claim 19, wherein the RIM process comprises the steps of:
(1) Adding one or more of functional filler, comonomer and auxiliary agent into dicyclopentadiene as A liquid;
(2) Taking the catalyst composition as a solution B, and adding one or more of functional filler, comonomer and auxiliary agent;
(3) Introducing the solution A and the solution B into a material storage system for later use;
(4) The solution A and the solution B are subjected to reaction injection molding in RIM equipment;
(5) And curing to obtain the resin material.
21. The method according to claim 17 or 20,
in the step (3), the storage system is a storage tank of the RIM equipment;
and/or in the step (3), the temperature of the material storage system is-10 ℃ to 40 ℃;
and/or in the step (4), the mass ratio of the solution A to the solution B is 1;
and/or, in the step (4), mixing the solution A and the solution B on line and injecting the mixture into a mold to complete reaction injection molding;
and/or in the step (4), the glue injection speed of the reaction injection molding is 200mL/min-100L/min;
and/or, in the step (4), the glue injection pressure of the reaction injection molding is 0.1-20bar;
and/or, in the step (5), the temperature during curing is 60-120 ℃;
and/or, in the step (5), the curing time is 1-120min.
22. The method of claim 21,
in the step (3), the temperature of the material storage system is-5 ℃ to 25 ℃;
and/or in the step (4), the mass ratio of the solution A to the solution B is (1);
and/or in the step (4), the glue injection speed of the reaction injection molding is 200mL/min-2000mL/min;
and/or, in the step (4), the glue injection pressure of the reaction injection molding is 1-15bar;
and/or, in the step (5), the temperature during curing is 70-100 ℃.
23. The method according to claim 22, wherein the mass ratio of the solution A to the solution B is 2.
24. A resin material produced by the production method according to any one of claims 15 to 23.
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| JP2011017028A (en) * | 1999-09-01 | 2011-01-27 | Materia Inc | Metathesis polymerization catalyst liquid |
| WO2015115936A1 (en) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Composition for producing a composite material, composite material and method for producing same |
| CN106243279A (en) * | 2016-08-03 | 2016-12-21 | 上海克琴科技有限公司 | Multicolour, ageing-resistant exempting from spray Polydicyclopentadiencomposite composite material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011017028A (en) * | 1999-09-01 | 2011-01-27 | Materia Inc | Metathesis polymerization catalyst liquid |
| WO2015115936A1 (en) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Composition for producing a composite material, composite material and method for producing same |
| CN106243279A (en) * | 2016-08-03 | 2016-12-21 | 上海克琴科技有限公司 | Multicolour, ageing-resistant exempting from spray Polydicyclopentadiencomposite composite material and its preparation method and application |
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