CN112745431B - Cycloolefin copolymer and preparation method thereof - Google Patents

Cycloolefin copolymer and preparation method thereof Download PDF

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CN112745431B
CN112745431B CN202011538511.0A CN202011538511A CN112745431B CN 112745431 B CN112745431 B CN 112745431B CN 202011538511 A CN202011538511 A CN 202011538511A CN 112745431 B CN112745431 B CN 112745431B
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copolymer
cycloolefin
norbornene
structural unit
cycloolefin copolymer
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CN112745431A (en
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廖恒
赵环宇
刘阳
左洪亮
陈炳琳
黄杰
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Guangdong Teju New Materials Technology Co ltd
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Guangdong Huajinda New Material Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Abstract

The present invention relates to the field of olefin polymerization, and more particularly, to a cycloolefin copolymer composed of structural units and a process for preparing the same
Figure DDA0002854240060000011
Structural unit
Figure DDA0002854240060000012
Structural unit

Description

Cycloolefin copolymer and preparation method thereof
Technical Field
The present invention relates to the field of olefin polymerization, and more particularly, to a cycloolefin copolymer and a preparation method thereof.
Background
The cycloolefin copolymer is an amorphous thermoplastic polymer prepared by taking part in addition copolymerization of cycloolefin monomers, has the characteristics of good transparency, good heat resistance, low water absorption, chemical corrosion resistance and the like, has the advantages of high mechanical strength, good dimensional stability, low dielectric constant and the like, and is widely applied to the fields of optical materials, communication equipment, medical materials, packaging materials and the like.
According to the known literature, cycloolefin copolymers can be prepared with metallocene catalysts (CN 95107662, CN 94120496) or other non-metallocene transition metal catalysts (CN 201610040109), but the polymerization process can result in partially crystalline polyethylene segments of the polymerization system due to unavoidable homopolymerization of ethylene, which affects the transparency of the polymer. Meanwhile, the heat resistance of the cycloolefin copolymer is to be improved.
Disclosure of Invention
In view of the problems of the prior art, a first aspect of the present invention provides a cycloolefin copolymer which is composed of the structural unit (a)
Figure BDA0002854240050000011
Structural unit (b)/(H)>
Figure BDA0002854240050000012
Structural unit (c)/(H)>
Figure BDA0002854240050000013
The structural unit (a) has a repetition number x of 0-3 in the molecular chain of the copolymer unit, the structural unit (b) has a repetition number y of 1-3 in the molecular chain of the copolymer unit, the structural unit (c) has a repetition number z of 1-3 in the molecular chain of the copolymer unit, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar group; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2.
As a preferable technical scheme of the invention, R is any one of hydrogen, methyl, ethyl, isopropyl, n-butyl, hydroxyl, carboxyl, methyl ester group, amino, dimethylamino, trimethylsilyl and trimethoxysilyl.
As a preferable technical scheme of the invention, the preparation raw materials of the cycloolefin copolymer comprise ethylene, norbornene cycloolefin monomers shown in the formula (I), a catalyst shown in the formula (II) and a cocatalyst, wherein,
Figure BDA0002854240050000021
formula (I), I>
Figure BDA0002854240050000022
Formula (II); m is 0 or 1, R is any one of hydrogen, alkyl and polar group, R 1 -R 5 、R 8 -R 12 Are respectively and independently any one of hydrogen, alkyl and aryl, R 6 、R 7 Each independently represents any one of hydrogen, alkyl and aryl or is combined into the same cyclic substituent, mt represents nickel or palladium, and X represents halogen or substituted or unsubstituted alkyl.
As a preferred embodiment of the present invention, the R 1 、R 5 、R 8 、R 12 Are respectively and independently any one of methyl, isopropyl, phenyl and benzhydryl, R 2 -R 4 、R 9 -R 11 Is hydrogen, R 6 、R 7 Each independently represents any one of hydrogen, methyl, phenyl, acenaphthenyl and dibenzo-barrel alkenyl, and X represents any one of chlorine, bromine, methyl, benzyl and substituted alkyl.
As a preferable embodiment of the present invention, the norbornene-type cycloolefin monomer is any one of norbornene, alkyl-substituted norbornene, methyl norbornene, ethylnorbornene, n-propyl norbornene, isopropyl norbornene, n-butyl norbornene, hydroxy norbornene, carboxy norbornene, methyl ester norbornene, amino norbornene, alkylamino norbornene, silyl norbornene, tetracyclododecene, alkyl tetracyclododecene, hydroxy tetracyclododecene, carboxy tetracyclododecene, ester tetracyclododecene, amino tetracyclododecene, alkylamino tetracyclododecene, and silyl tetracyclododecene.
As a preferable technical scheme of the invention, the cocatalyst is alkyl aluminoxane, the structure is (-AlM-O-) n, n is any positive integer, and M is any one of methyl, ethyl, isobutyl and n-octyl.
As a preferred embodiment of the present invention, the cycloolefin copolymer is prepared from a starting material which also includes an inert hydrocarbon solvent.
As a preferred embodiment of the present invention, the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon, preferably n-hexane, cyclohexane, n-heptane, C 6 -C 12 One or more of the mixed alkanes, benzene, toluene.
In a second aspect, the present invention provides a process for preparing the cycloolefin copolymer, comprising: ethylene, norbornene cycloolefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized in the presence or absence of inert hydrocarbon solvent at 0-100deg.C and 0.1-100 atm.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the post-transition metal catalyst with a specific structure and a 'chain walking' characteristic, avoids the generation of crystalline ethylene chain segments, improves the transparency of the obtained copolymer, introduces a branched structure into a polymer chain, has higher glass transition temperature than that of a metallocene ethylene/norbornene copolymer under the same norbornene content, and improves the thermal stability of the polymer. Meanwhile, the catalyst system has good tolerance to water, oxygen and polar groups, can prepare cycloolefin copolymer with polar groups, and has wider application prospect.
Detailed Description
The first aspect of the present invention provides the cycloolefin copolymer which is composed of the structural unit (a)
Figure BDA0002854240050000031
Structural unit (b)/(H)>
Figure BDA0002854240050000032
Structural unit (c)/(H)>
Figure BDA0002854240050000033
The structural unit (a) has a repetition number x of 0-3 in the molecular chain of the copolymer unit, the structural unit (b) has a repetition number y of 1-3 in the molecular chain of the copolymer unit, the structural unit (c) has a repetition number z of 1-3 in the molecular chain of the copolymer unit, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar group; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2.
Molecular weight distribution: the polymer and the low molecular weight compound are different, and do not have fixed molecular weight, but are a mixed system of different molecular weight homologs. The polymer molecular weight is thus an average value, with a distribution concept. This heterogeneity in molecular weight is referred to as the polydispersity of the polymer. The polydispersity of a polymer sample is typically characterized by a polydispersity, α, which is the ratio of the weight average molecular weight to the number average molecular weight or the ratio of the Z average molecular weight to the weight average molecular weight.
In one embodiment, R is any one of hydrogen, methyl, ethyl, isopropyl, n-butyl, hydroxyl, carboxyl, methyl ester group, amino, dimethylamino, trimethylsilyl, trimethoxysilyl.
In one embodiment, the raw materials for preparing the cycloolefin copolymer comprise ethylene, norbornene cycloolefin monomers shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst, wherein,
Figure BDA0002854240050000041
the compound of formula (I),
Figure BDA0002854240050000042
formula (II); m is 0 or 1, R is any one of hydrogen, alkyl and polar group, R 1 -R 5 、R 8 -R 12 Are respectively and independently any one of hydrogen, alkyl and aryl, R 6 、R 7 Each independently represents any one of hydrogen, alkyl and aryl or is combined into the same cyclic substituent,mt is nickel or palladium, X is halogen, substituted or unsubstituted alkyl.
Preferably, said R 1 、R 5 、R 8 、R 12 Are respectively and independently any one of methyl, isopropyl, phenyl and benzhydryl, R 2 -R 4 、R 9 -R 11 Is hydrogen, R 6 、R 7 Each independently represents any one of hydrogen, methyl, phenyl, acenaphthenyl and dibenzo-cycloalkenyl, and X represents any one of chlorine, bromine, methyl, benzyl and substituted alkyl; the catalyst obtained at this time has good reaction controllability in the process of catalyzing polymerization, can better avoid the generation of crystalline ethylene chain segments, improves the probability of transparency of the obtained copolymer, has better chain running characteristic under the condition, has a properly beneficial branched chain structure on the copolymer chain, and obtains better heat resistance.
In one embodiment, the norbornene-type cycloolefin monomer is any one of norbornene, alkyl substituted norbornene, methyl norbornene, ethylnorbornene, n-propyl norbornene, isopropyl norbornene, n-butyl norbornene, hydroxy norbornene, carboxy norbornene, methyl ester norbornene, amino norbornene, alkylamino norbornene, silyl norbornene, tetracyclododecene, alkyl tetracyclododecene, hydroxy tetracyclododecene, carboxy tetracyclododecene, ester tetracyclododecene, amino tetracyclododecene, alkylamino tetracyclododecene, and silyl tetracyclododecene.
Preferably, the norbornene-type cycloolefin monomer is norbornene or tetracyclododecene.
In the preparation process of the cycloolefin copolymer, the norbornene and the tetracyclododecene have simple structure, are easy to synthesize and have high reaction activity, and the obtained ethylene/norbornene copolymer or ethylene/tetracyclododecene copolymer has regular structure and excellent performance.
In one embodiment, the cocatalyst is an alkylaluminoxane having the structure (-AlM-O-) n, n being any positive integer.
Preferably, M is any one of methyl, ethyl, isobutyl, n-octyl; more preferably, M is methyl or isobutyl.
In the preparation process of the cycloolefin copolymer, when M is methyl or isobutyl, the synergism with the catalyst is better.
In one embodiment, the starting material for the preparation of the cycloolefin copolymer further comprises an inert hydrocarbon solvent.
Preferably, the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon; further preferably, the inert hydrocarbon solvent is selected from the group consisting of n-hexane, cyclohexane, n-heptane, C 6 -C 12 One or more of mixed alkane, benzene, toluene; more preferably, the inert hydrocarbon solvent is n-heptane and/or toluene.
In one embodiment, the ethylene content is based on adjusting the ethylene content such that the pressure is 0.1 to 100 atm.
The content of the norbornene-type cycloolefin monomer in the present application is not particularly limited, and may be routinely selected by those skilled in the art as required.
In one embodiment, the norbornene-type cycloolefin monomer is present in the cycloolefin copolymer in a proportion of 20 to 35mol%.
The concentrations of catalyst and cocatalyst in the present application are not particularly limited, and may be routinely selected by one skilled in the art.
In one embodiment, the catalyst concentration is from 0.1 to 10. Mu. Mol/L.
In one embodiment, the concentration of the cocatalyst is in the range of 0.1 to 10mmol/L.
In a second aspect, the present invention provides a process for preparing the cycloolefin copolymer, comprising: ethylene, norbornene cycloolefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized in the presence or absence of inert hydrocarbon solvent at 0-100deg.C and 0.1-100 atm.
In one embodiment, the method of preparing the cyclic olefin copolymer includes: ethylene, norbornene cycloolefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized under the condition of existence or nonexistence of inert hydrocarbon solvent at 0-100 ℃ and 0.1-100atm to obtain reaction liquid, the reaction liquid is added into hydrochloric acid/ethanol solution to terminate the reaction, the separated copolymer is filtered, washed by ethanol and dried to obtain the catalyst.
Preferably, the preparation method of the cycloolefin copolymer comprises the following steps: ethylene, norbornene cycloolefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized for 30min under the condition of existence or nonexistence of inert hydrocarbon solvent at 20-80 ℃ and 1-30atm to obtain reaction liquid, the reaction liquid is added into 10vol% hydrochloric acid/ethanol solution to terminate the reaction, the separated copolymer is filtered, washed by ethanol and dried in vacuum at 80 ℃ for 24h to obtain the catalyst.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not limitative. The raw materials used in the following examples are all commercially available, unless otherwise specified.
The cycloolefin monomer content in the copolymer was measured by nuclear magnetic resonance spectroscopy using deuterated chloroform as a solvent. The molecular weight and molecular weight distribution of the copolymer were determined by high temperature gel chromatography (HTGPC) with 1,2, 4-trichlorobenzene as the solvent. The glass transition temperature of the copolymer was measured by a Differential Scanning Calorimeter (DSC).
Example 1
Example 1 of the present invention provides the cycloolefin copolymer, which is prepared as follows:
38mL of the prepared 0.30mol/L norbornene toluene solution and 1mL of 10wt% methylaluminoxane toluene solution (cocatalyst) were added to a 100mL glass bottle under a nitrogen atmosphere, the ethylene pressure was adjusted to 1atm, and the mixture was equilibrated at 20℃for 30 minutes; then 1mL of 1. Mu. Mol/mL toluene solution of catalyst 1 was added to start the reaction, and the ethylene pressure was kept at 1atm, and the polymerization reaction was carried out for 30min; the reaction mixture was added to a 10vol% hydrochloric acid/ethanol solution to terminate the reaction, and the precipitated copolymer was filtered, washed with ethanol, and dried under vacuum at 80℃for 24 hours to obtain 0.55g of a copolymer.
The structure of the catalyst 1 is that
Figure BDA0002854240050000061
R in catalyst 1 1 -R 12 The physical properties of Mt and the copolymer are shown in Table 1 below.
Example 2
Example 2 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1, except that catalyst 2 is used in place of catalyst 1, and the weight of the copolymer is 0.52g.
The structure of the catalyst 2 is that
Figure BDA0002854240050000062
R in catalyst 2 1 -R 12 The physical properties of Mt and the copolymer are shown in Table 1 below.
Example 3
Example 3 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1, except that catalyst 3 is used in place of catalyst 1, and the weight of the copolymer is 0.72g.
The structure of the catalyst 3 is that
Figure BDA0002854240050000071
R in catalyst 3 1 -R 12 The physical properties of Mt and the copolymer are shown in Table 1 below.
Example 4
Example 4 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1, except that catalyst 4 is used in place of catalyst 1, and the copolymer weight is 0.46g.
The structure of the catalyst 4 is that
Figure BDA0002854240050000072
R in catalyst 4 1 -R 12 The physical properties of Mt and the copolymer are shown in Table 1 below.
Example 5
Example 5 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1, except that catalyst 5 is used in place of catalyst 1, and the weight of the copolymer is 0.58g.
The structure of the catalyst 5 is that
Figure BDA0002854240050000073
R in catalyst 5 1 -R 12 The physical properties of Mt and the copolymer are shown in Table 1 below.
TABLE 1
Figure BDA0002854240050000074
Figure BDA0002854240050000081
Example 6
Example 6 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1 except that norbornene is replaced by methylnorbornene, and the weight of the resulting copolymer is 0.42g.
The physical properties of the copolymer are described in Table 2 below.
Example 7
Example 7 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1 except that norbornene is replaced by methylnorbornene, and the weight of the resultant copolymer is 0.56g.
The physical properties of the copolymer are described in Table 2 below.
Example 8
Example 8 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1 except that dimethylaminonorbornene is used instead of norbornene, and the weight of the resultant copolymer is 0.49g.
The physical properties of the copolymer are described in Table 2 below.
Example 9
Example 9 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1 except that trimethoxysilylnorbornene is used instead of norbornene, and the weight of the resultant copolymer is 0.55g.
The physical properties of the copolymer are described in Table 2 below.
Example 10
Example 10 of the present invention provides the cycloolefin copolymer, the production process of which is carried out in the same manner as example 1 except that tetracyclododecene is used instead of norbornene, and the weight of the resultant copolymer is 0.50g.
The physical properties of the copolymer are described in Table 2 below.
TABLE 2
Examples Cycloolefin monomer content mol% Glass transition temperature (DEG C)
6 28 79
7 23 65
8 21 60
9 26 76
10 20 57
Example 11
Example 11 of the present invention provides the cycloolefin copolymer, which is prepared as follows:
200mL of a pre-prepared toluene solution of 2.00mol/L norbornene and 5mL of a 10wt% toluene solution of methylaluminoxane are added into a 500mL glass bottle under a nitrogen atmosphere, the ethylene pressure is regulated to be 30atm, and the mixture is stirred and balanced for 30min at 80 ℃; then 5mL of 1 mu mol/mL toluene solution of catalyst 1 was added to start the reaction, and the ethylene pressure was kept at 30atm, and the polymerization reaction was carried out for 30min; the reaction mixture was added to a 10vol% hydrochloric acid/ethanol solution to terminate the reaction, and the precipitated copolymer was filtered, washed with ethanol, and dried under vacuum at 80℃for 24 hours to obtain 56.2g of a copolymer. The glass transition temperature of the copolymer was 73℃and the molecular weight was 25.2kDa, and the molecular weight distribution was 1.8.
Example 12
Example 12 of the present invention provides a cycloolefin copolymer, which is different from example 11 in that a norbornene toluene solution having a concentration of 3.00mol/L is used instead of a norbornene toluene solution of 2.00mol/L, and 42.3g of the copolymer having a glass transition temperature of 95℃and a molecular weight of 31.8kDa and a molecular weight distribution of 1.9 is obtained.
Example 13
Example 13 of the present invention provides a cycloolefin copolymer, which was carried out as in example 11, except that a norbornene toluene solution having a concentration of 5.00mol/L was used instead of 2.00mol/L of the norbornene toluene solution, and 38.6g of the copolymer having a glass transition temperature of 133℃and a molecular weight of 37.4kDa and a molecular weight distribution of 1.7 was obtained.
Example 14
Example 14 of the present invention provides a cycloolefin copolymer, which was carried out as in example 11, except that a norbornene toluene solution having a concentration of 6.00mol/L was used instead of 2.00mol/L of the norbornene toluene solution, and 32.7g of the copolymer having a glass transition temperature of 165℃and a molecular weight of 45.6kDa and a molecular weight distribution of 1.8 was obtained.
Example 15
Example 15 of the present invention provides a cycloolefin copolymer, which is specified as in example 11 except that isobutylaluminoxane is used instead of methylaluminoxane, 50.5g of a copolymer having a glass transition temperature of 75℃and a molecular weight of 19.2kDa and a molecular weight distribution of 2.0 is obtained.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The appended claims are intended to claim the broadest possible scope and the embodiments presented herein are merely illustrative of selected implementations based on combinations of all possible embodiments. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.

Claims (8)

1. A process for producing a cycloolefin copolymer, characterized in that the cycloolefin copolymer is composed of the structural unit (a)
Figure 523886DEST_PATH_IMAGE001
Structural unit (b)/(b)>
Figure 587657DEST_PATH_IMAGE002
Structural unit (c)>
Figure 520977DEST_PATH_IMAGE003
The structural unit (a) has a repetition number x of 0-3 in the molecular chain of the copolymer unit, the structural unit (b) has a repetition number y of 1-3 in the molecular chain of the copolymer unit, the structural unit (c) has a repetition number z of 1-3 in the molecular chain of the copolymer unit, and the structural unit (a), the structural unit (b) and the structural unit (c) are randomly distributed in the copolymer chain; k is 0-3, m is 0 or 1, R is any one of hydrogen, alkyl and polar group; the glass transition temperature of the cycloolefin copolymer is 50-200 ℃, the molecular weight is 15-50kDa, and the molecular weight distribution is 1.5-2;
the preparation raw materials of the cycloolefin copolymer comprise ethylene, norbornene cycloolefin monomers shown in a formula (I), a catalyst shown in a formula (II) and a cocatalyst, wherein,
Figure 986594DEST_PATH_IMAGE004
formula (I), I>
Figure 714378DEST_PATH_IMAGE005
Formula (II); m is 0 or 1, R is any one of hydrogen, alkyl and polar group; r is R 1 、R 5 、R 8 、R 12 Are respectively and independently any one of methyl, isopropyl, phenyl and benzhydryl, R 2 -R 4 、R 9 -R 11 Is hydrogen, R 6 、R 7 Each independently represents any one of hydrogen, methyl, phenyl, acenaphthene and dibenzo-barrel alkenyl, mt represents nickel or palladium, and X represents any one of chlorine, bromine, methyl, benzyl and substituted alkyl.
2. The method for producing a cycloolefin copolymer according to claim 1, characterized in that R is any one of hydrogen, methyl, ethyl, isopropyl, n-butyl, hydroxyl, carboxyl, methyl ester group, amino group, dimethylamino group, trimethylsilyl group, trimethoxysilyl group.
3. The method for preparing a cycloolefin copolymer according to claim 2, wherein the norbornene-based cycloolefin monomer is any one of norbornene, methylnorbornene, ethylnorbornene, n-propylnorbornene, isopropylnorbornene, n-butylnorbornene, hydroxynorbornene, carboxynorbornene, methylester-based norbornene, aminonorbornene, alkylaminonorbornene, silylnorbornene, tetracyclododecene, alkyltetracyclododecene, hydroxytetracyclododecene, carboxytetracyclododecene, estertetracyclododecene, aminotetracyclododecene, alkylamino tetracyclododecene, and silyltercyclododecene.
4. The process for preparing cycloolefin copolymer according to any of claims 1 to 3, characterized in that the cocatalyst is alkylaluminoxane, the structure is (-AlM-O-) n, n is any positive integer, and M is any of methyl, ethyl, isobutyl and n-octyl.
5. The process for producing a cycloolefin copolymer according to claim 4, characterized in that the raw material for producing the cycloolefin copolymer further comprises an inert hydrocarbon solvent.
6. The process for producing a cycloolefin copolymer according to claim 5, characterized in that the inert hydrocarbon solvent is an alkane and/or an aromatic hydrocarbon.
7. The process for preparing cycloolefin copolymers according to claim 6, characterized in that the inert hydrocarbon solvent is selected from the group consisting of n-hexane, cyclohexane, n-heptane, C 6 -C 12 One or more of the mixed alkanes, benzene, toluene.
8. A process for the preparation of a cyclic olefin copolymer according to any one of claims 1 to 3, characterized in that it comprises: ethylene, norbornene cycloolefin monomer shown in formula (I), catalyst shown in formula (II) and cocatalyst are copolymerized in the presence or absence of inert hydrocarbon solvent at 0-100deg.C and 0.1-100 atm.
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