CN106478854B - Poly- (1,9- decadinene) and preparation method thereof - Google Patents
Poly- (1,9- decadinene) and preparation method thereof Download PDFInfo
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- CN106478854B CN106478854B CN201610885069.6A CN201610885069A CN106478854B CN 106478854 B CN106478854 B CN 106478854B CN 201610885069 A CN201610885069 A CN 201610885069A CN 106478854 B CN106478854 B CN 106478854B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/20—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
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Abstract
The present invention relates to olefin catalytic polymerization fields, it is desirable to provide a kind of poly- (1,9- decadinene) and preparation method thereof.This poly- (1,9- decadinene) molecule in carbon-carbon double bond content be 0.63~2.68mol%, contain 64~72 branches in every 1000 carbon, wherein 13.4~39.4mol% is methyl branch, 60.6~86.6mol% is amyl or longer alkyl branches.The present invention is with (alpha-diimine) nickel olefin polymerization catalyst catalysis 1, the polymerization of 9- decadinene, 1 in polymerization process, 9- decadinene will not crosslink reaction, poly- (the 1 of preparation, 9- decadinene) it is soluble in the common solvents such as tetrahydrofuran, toluene, dimethylbenzene, methylene chloride, hexane, heptane, octane, it can also melt at a proper temperature.There is partial double bond to be not engaged in polymerization in the course of the polymerization process, keeps down in the polymer.These double bonds can be used as reactive group and carry out the reactions such as epoxidation, click chemistry reaction, vulcanization, be used to prepare many novel polymer.
Description
Technical field
The present invention relates to olefin catalytic polymerization fields, and in particular to a kind of poly- (1,9- decadinene) and preparation method thereof.
Background technique
Alkadienes refers to the hydrocarbon compound containing two carbon-carbon double bonds, general formula CnH2(n-1), belong to unsaturated hydrocarbons.According to
The relative position of two double bonds can be divided into molecule: (1) allenyl: two double bonds are connected in the same carbon atom in molecule
On；(2) isolate alkadienes: two double bonds are separated by more than one singly-bound in molecule；(3) conjugated diene: two in molecule
A double bond is separated by a singly-bound.Allenyl number is seldom.Conjugated diene is mostly important, has certain different from general
The property of logical alkene.Such as molecule it is more stable, 1,4- addition, polymerization easier than common alkene can occur.Conjugated diene is closing
At particularly significant on rubber, such as: 1,3-butadiene self-polymerization at butadiene rubber, with styrene copolymerized butadiene-styrene rubber, with
Acrylonitrile compolymer obtains nitrile rubber.Isoprene (i.e. 2- methyl-1,3- butadiene) self-polymerization is at isoprene rubber.Isolated diene
Hydrocarbon (such as 1,5- hexadiene, 1,9- decadinene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene etc.) alkene with
Hydrocarbon property is similar.Since two double bonds are separated by more than one singly-bound in their molecule, self-polymerization is easy to occur
Crosslinking, so isolated alkadienes is typically limited to only as crosslinking agent.Only dicyclopentadiene can be anti-by ring-opening metathesis polymerization
Polydicyclopentadiene should be made, be a kind of cross-linked three D reticular Structural Engineering plastics.
Therefore, how to select suitable catalyst, control polymerizing condition, make to isolate during alkadienes self-polymerization not
It crosslinks, but also a certain amount of double bond can be left in the polymer, then become a difficult project.These double bonds can be with
The reactions such as epoxidation, click chemistry reaction, vulcanization are carried out as reactive group, are used to prepare many novel polymer.
Summary of the invention
The problem to be solved in the present invention is to overcome deficiency in the prior art, provide a kind of poly- (1,9- decadinene) and its
Preparation method.
In order to solve the above technical problems, solution of the invention is:
A kind of poly- (1,9- decadinene) is provided, is the homopolymer of 1,9- decadinene；The molecular structure of poly- (1,9- decadinene)
Shown in schematically as follows:
The content of carbon-carbon double bond is 0.63~2.68mol% in molecule, contains 64~72 branches in every 1000 carbon,
In 13.4~39.4mol% be methyl branch, 60.6~86.6mol% be amyl or longer alkyl branches.
In the present invention, the number-average molecular weight of poly- (1, the 9- decadinene) is 1.74 × 104~5.85 × 104G/mol, molecule
Measuring profile exponent is 1.81~3.86, and glass transition temperature is -12.1~-27.7 DEG C.
Invention further provides the preparation methods of poly- (1,9- decadinene) above-mentioned, comprising the following steps:
Anhydrous, anaerobic 1,9- decadinene is taken, is placed in the 50mLSchlenk bottle under nitrogen protection, anhydrous, anaerobic is added
Solvent, magneton stirring under be heated to 20~60 DEG C after constant temperature, is formed concentration for 0.2~2.5mol/L 1,9- decadinene it is molten
Liquid；Then it is added as the aluminium diethyl monochloride of co-catalyst, ethyl aluminum dichloride, sesquialter aluminium ethide or methylaluminoxane, and
(alpha-diimine) nickel olefin polymerization catalyst, the molar ratio of co-catalyst and (alpha-diimine) nickel olefin polymerization catalyst is 50~
1000, the molar ratio of alkadienes and (alpha-diimine) nickel olefin polymerization catalyst is 800~10000；Polymerization reaction 0.5~10 is small
Shi Hou is terminated with acidic ethanol and is polymerize and be precipitated out polymer；Collected polymer moves to dry in 40 DEG C of vacuum drying oven
To constant weight to get arrive poly- (1,9- decadinene).
In the present invention, the solvent is any one in normal heptane, toluene, methylene chloride or trichloro-benzenes.
In the present invention, the structural formula of described (alpha-diimine) nickel olefin polymerization catalyst is shown below:
In the formula, R H, CH3、
In the present invention, 1, the 9- decadinene can be dissolved in tetrahydrofuran, toluene, dimethylbenzene, methylene chloride, hexane, heptan
Alkane or octane, and can be melted under the conditions of 50 DEG C of temperatures above.
Compared with prior art, the beneficial effects of the present invention are:
1, it is polymerize with (alpha-diimine) nickel olefin polymerization catalyst catalysis 1,9- decadinene, 1,9- decadinene in polymerization process
Will not crosslink reaction, poly- (1, the 9- decadinene) of preparation be soluble in tetrahydrofuran, toluene, dimethylbenzene, methylene chloride,
In the common solvents such as hexane, heptane, octane, it can also melt at a proper temperature.
2,1,9- decadinene has partial double bond to be not engaged in polymerization in the course of the polymerization process, keeps down in the polymer.
These double bonds can be used as reactive group and carry out the reactions such as epoxidation, click chemistry reaction, vulcanization, be used to prepare many novel
Polymer.
Specific embodiment
The present invention, but following implementations further can be clearly parsed by the specific embodiment of invention now given below
Example is not limitation of the invention.
Embodiment 1
Take that 0.552g (0.004mol) is anhydrous, 1,9- decadinene of anaerobic, the 50mLSchlenk bottle being placed under nitrogen protection
In, it is added that 20mL is anhydrous, toluene of anaerobic, magneton stirring is heated to 35 DEG C and constant temperature, sequentially adds mono- chlorine diethyl of 1mmol
Aluminium and 5 μm of ol catalyst 2 ((alpha-diimine) nickel olefin polymerization catalyst, R CH3), after polymerization 10 hours, with acidic ethanol end
Only it polymerize and is precipitated out polymer, collected polymer, it is put into 40 DEG C of vacuum drying oven and is dried to constant weight.It must polymerize
Object 0.17g, number-average molecular weight 1.74 × 104G/mol, molecular weight distributing index 2.38 contain 66 branches in every 1000 carbon,
Wherein 24 are methyl branch, and 42 are amyl or longer branch, and the content of carbon-carbon double bond is 0.63mol%, and vitrifying turns
Temperature is -12.1 DEG C.
Embodiment 2
Take that 1.38g (0.01mol) is anhydrous, 1,9- decadinene of anaerobic, remaining condition is the same as embodiment 1.Obtain polymer
0.21g, number-average molecular weight 3.89 × 104G/mol, molecular weight distributing index 3.86 contain 66 branches in every 1000 carbon,
In 26 be methyl branch, 40 are amyl or longer branch, and the content of carbon-carbon double bond is 1.17mol%, glass transition
Temperature is -13.6 DEG C.
Embodiment 3
Take that 2.76g (0.02mol) is anhydrous, 1,9- decadinene of anaerobic, remaining condition is the same as embodiment 1.Obtain polymer
0.26g, number-average molecular weight 4.5 × 104G/mol, molecular weight distributing index 2.28 contain 65 branches in every 1000 carbon,
In 23 be methyl branch, 42 are amyl or longer branch, and the content of carbon-carbon double bond is 1.92mol%, glass transition
Temperature is -17.6 DEG C.
Embodiment 4
Take that 4.14g (0.03mol) is anhydrous, 1,9- decadinene of anaerobic, remaining condition is the same as embodiment 1.Obtain polymer
0.25g, number-average molecular weight 5.85 × 104G/mol, molecular weight distributing index 2.41 contain 66 branches in every 1000 carbon,
In 15 be methyl branch, 51 are amyl or longer branch, and the content of carbon-carbon double bond is 2.51mol%, glass transition
Temperature is -23.5 DEG C.
Embodiment 5
Take that 6.90g (0.05mol) is anhydrous, 1,9- decadinene of anaerobic, remaining condition is the same as embodiment 1.Obtain polymer
0.20g, number-average molecular weight 3.01 × 104G/mol, molecular weight distributing index 2.65 contain 67 branches in every 1000 carbon,
In 9 be methyl branch, 58 are amyl or longer branch, and the content of carbon-carbon double bond is 2.68mol%, glass transition temperature
Degree is -27.7 DEG C.
Embodiment 6
Polymerization time shortens to 0.5 hour, remaining condition is the same as embodiment 1.Obtain polymer 0.13g, number-average molecular weight 3.09
×104G/mol, molecular weight distributing index 1.99 contain 64 branches in every 1000 carbon, wherein 22 are methyl branch, 42
A is amyl or longer branch, and the content of carbon-carbon double bond is 1.82mol%, and glass transition temperature is -20.5 DEG C.
Embodiment 7
Polymerization time shortens to 1 hour, remaining condition is the same as embodiment 1.Polymer 0.15g, number-average molecular weight 3.11 ×
104G/mol, molecular weight distributing index 2.84 contain 64 branches in every 1000 carbon, wherein 22 are methyl branch, 42
For amyl or longer branch, the content of carbon-carbon double bond is 1.76mol%, and glass transition temperature is -21.5 DEG C.
Embodiment 8
Polymerization time shortens to 2 hours, remaining condition is the same as embodiment 1.Polymer 0.22g, number-average molecular weight 3.57 ×
104G/mol, molecular weight distributing index 3.46 contain 70 branches in every 1000 carbon, wherein 25 are methyl branch, 45
For amyl or longer branch, the content of carbon-carbon double bond is 1.65mol%, and glass transition temperature is -18.2 DEG C.
Embodiment 9
Polymerization time shortens to 5 hours, remaining condition is the same as embodiment 1.Polymer 0.25g, number-average molecular weight 3.95 ×
104G/mol, molecular weight distributing index 1.81 contain 70 branches in every 1000 carbon, wherein 26 are methyl branch, 44
For amyl or longer branch, the content of carbon-carbon double bond is 1.91mol%, and glass transition temperature is -16.7 DEG C.
Embodiment 10
Change solvent into normal heptane, remaining condition is the same as embodiment 3.Polymer 0.16g, number-average molecular weight 3.37 ×
104G/mol, molecular weight distributing index 2.70 contain 66 branches in every 1000 carbon, wherein 25 are methyl branch, 41
For amyl or longer branch, the content of carbon-carbon double bond is 1.66mol%, and glass transition temperature is -16.8 DEG C.
Embodiment 11
Change solvent into methylene chloride, remaining condition is the same as embodiment 3.Polymer 0.31g, number-average molecular weight 4.92 ×
104G/mol, molecular weight distributing index 2.20 contain 68 branches in every 1000 carbon, wherein 26 are methyl branch, 42
For amyl or longer branch, the content of carbon-carbon double bond is 1.61mol%, and glass transition temperature is -16.3 DEG C.
Embodiment 12
Change solvent into trichloro-benzenes, remaining condition is the same as embodiment 3.Polymer 0.35g, number-average molecular weight 5.17 ×
104G/mol, molecular weight distributing index 2.15 contain 72 branches in every 1000 carbon, wherein 26 are methyl branch, 46
For amyl or longer branch, the content of carbon-carbon double bond is 2.19mol%, and glass transition temperature is -17.0 DEG C.
Embodiment 13
Change co-catalyst into ethyl aluminum dichloride, the molar ratio of ethyl aluminum dichloride and catalyst is 50, remaining condition is the same as real
Apply example 3.Obtain polymer 0.41g, number-average molecular weight 3.74 × 104G/mol, molecular weight distributing index 2.01, in every 1000 carbon
Containing 68 branches, wherein 25 are methyl branch, 43 are amyl or longer branch, and the content of carbon-carbon double bond is
1.98mol%, glass transition temperature are -16.8 DEG C.
Embodiment 14
Change co-catalyst into sesquialter aluminium ethide, the molar ratio of sesquialter aluminium ethide and catalyst is 100, remaining condition is the same as real
Apply example 3.Obtain polymer 0.38g, number-average molecular weight 4.32 × 104G/mol, molecular weight distributing index 2.13, in every 1000 carbon
Containing 66 branches, wherein 24 are methyl branch, 42 are amyl or longer branch, and the content of carbon-carbon double bond is
1.87mol%, glass transition temperature are -16.9 DEG C.
Embodiment 15
Change co-catalyst into methylaluminoxane, the molar ratio of methylaluminoxane and catalyst is 1000, remaining condition is same
Embodiment 3.Obtain polymer 0.29g, number-average molecular weight 5.42 × 104G/mol, molecular weight distributing index 2.01, every 1000 carbon
In contain 64 branches, wherein 22 are methyl branch, 42 are amyl or longer branch, and the content of carbon-carbon double bond is
2.07mol%, glass transition temperature are -17.1 DEG C.
Embodiment 16
Change catalyst into catalyst 1 ((alpha-diimine) nickel olefin polymerization catalyst, R H), the same embodiment of remaining condition
3.Obtain polymer 0.39g, number-average molecular weight 1.89 × 104G/mol, molecular weight distributing index 2.21 contain in every 1000 carbon
64 branches, wherein 23 are methyl branch, 41 are amyl or longer branch, and the content of carbon-carbon double bond is 1.99mol%,
Glass transition temperature is -14.8 DEG C.
Embodiment 17
Change catalyst into catalyst 1 ((alpha-diimine) nickel olefin polymerization catalyst, R H), polymerization temperature is changed to 20
DEG C, remaining condition is the same as embodiment 3.Obtain polymer 0.39g, number-average molecular weight 1.89 × 104G/mol, molecular weight distributing index
2.21,64 branches are contained in every 1000 carbon, wherein 23 are methyl branch, 41 are amyl or longer branch, carbon carbon
The content of double bond is 1.99mol%, and glass transition temperature is -14.8 DEG C.
Embodiment 18
Changing catalyst into catalyst 3, ((alpha-diimine) nickel olefin polymerization catalyst, R are), remaining condition is same
Embodiment 3.Obtain polymer 0.39g, number-average molecular weight 3.56 × 104G/mol, molecular weight distributing index 2.04, every 1000 carbon
In contain 66 branches, wherein 23 are methyl branch, 43 are amyl or longer branch, and the content of carbon-carbon double bond is
2.13mol%, glass transition temperature are -18.4 DEG C.
Embodiment 19
Changing catalyst into catalyst 4, ((alpha-diimine) nickel olefin polymerization catalyst, R are), polymerization temperature changes
It is 60 DEG C, remaining condition is the same as embodiment 3.Obtain polymer 0.28g, number-average molecular weight 3.67 × 104G/mol, molecular weight distribution refer to
Number 2.02 contains 70 branches in every 1000 carbon, wherein 25 are methyl branch, 45 are amyl or longer branch, carbon
The content of carbon double bond is 2.20mol%, and glass transition temperature is -27.4 DEG C.
Claims (6)
- A kind of 1. poly- (1,9- decadinene), it is characterised in that: poly- (1, the 9- decadinene) is the homopolymer of 1,9- decadinene；(1) content of carbon-carbon double bond is 0.63~2.68mol% in molecule；(2) in every 1000 carbon contain 64~72 branches, wherein 13.4~39.4mol% be methyl branch, 60.6~ 86.6mol% is amyl or longer alkyl branches.
- Poly- (1,9- decadinene) 2. according to claim 1, which is characterized in that the equal molecule of number of poly- (1, the 9- decadinene) Amount is 1.74 × 104~5.85 × 104G/mol, molecular weight distributing index are 1.81~3.86, and glass transition temperature is -12.1 ~-27.7 DEG C.
- The preparation method of poly- (1,9- decadinene) 3. described in claim 1, which comprises the following steps:Anhydrous, anaerobic 1,9- decadinene is taken, is placed in the 50mLSchlenk bottle under nitrogen protection, is added anhydrous, anaerobic molten Agent, constant temperature after being heated to 20~60 DEG C under magneton stirring form 1, the 9- decadinene solution that concentration is 0.2~2.5mol/L； Then it is added as the aluminium diethyl monochloride of co-catalyst, ethyl aluminum dichloride, sesquialter aluminium ethide or methylaluminoxane, and (α- Diimine) nickel olefin polymerization catalyst, the molar ratio of co-catalyst and (alpha-diimine) nickel olefin polymerization catalyst is 50~ The molar ratio of 1000,1,9- decadinene and (alpha-diimine) nickel olefin polymerization catalyst is 800~10000；Polymerization reaction 0.5~ After 10 hours, is terminated with acidic ethanol and polymerize and be precipitated out polymer；Collected polymer moves in 40 DEG C of vacuum drying oven Drying arrives poly- (1,9- decadinene) to constant weight.
- 4. preparation method according to claim 3, which is characterized in that the solvent is normal heptane, toluene, methylene chloride Or any one in trichloro-benzenes.
- 5. preparation method according to claim 3, which is characterized in that described (alpha-diimine) nickel olefin polymerization catalyst Structural formula be shown below:In the formula, R H, CH3、
- 6. preparation method according to claim 3, which is characterized in that 1, the 9- decadinene can be dissolved in tetrahydrofuran, Toluene, dimethylbenzene, methylene chloride, hexane, heptane or octane, and can be melted under the conditions of 50 DEG C of temperatures above.
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Citations (3)
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|---|---|---|---|---|
| CN1165151A (en) * | 1995-12-15 | 1997-11-19 | 联合碳化化学品及塑料技术公司 | Process for production of long-chain branched polyolefins |
| CN1181089A (en) * | 1995-01-24 | 1998-05-06 | 纳幕尔杜邦公司 | 'Alpha'-olefines and olefin polymers and processes therefor |
| CN104177528A (en) * | 2014-07-23 | 2014-12-03 | 浙江大学 | Ethylene/long-chain alpha-olefin copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8993680B2 (en) * | 2012-12-20 | 2015-03-31 | Exxonmobil Research And Engineering Company | Hyperbranched polyethylenes and a process for making |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181089A (en) * | 1995-01-24 | 1998-05-06 | 纳幕尔杜邦公司 | 'Alpha'-olefines and olefin polymers and processes therefor |
| CN1165151A (en) * | 1995-12-15 | 1997-11-19 | 联合碳化化学品及塑料技术公司 | Process for production of long-chain branched polyolefins |
| CN104177528A (en) * | 2014-07-23 | 2014-12-03 | 浙江大学 | Ethylene/long-chain alpha-olefin copolymer and preparation method thereof |
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