CN1033703C - Method capable of regulating molecular weight for preparing extra high molecular polyethylene - Google Patents
Method capable of regulating molecular weight for preparing extra high molecular polyethylene Download PDFInfo
- Publication number
- CN1033703C CN1033703C CN 93103156 CN93103156A CN1033703C CN 1033703 C CN1033703 C CN 1033703C CN 93103156 CN93103156 CN 93103156 CN 93103156 A CN93103156 A CN 93103156A CN 1033703 C CN1033703 C CN 1033703C
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- catalyst
- zncl
- titanium compound
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title abstract description 13
- 230000001105 regulatory effect Effects 0.000 title abstract description 7
- 239000004698 Polyethylene Substances 0.000 title 1
- -1 polyethylene Polymers 0.000 title 1
- 229920000573 polyethylene Polymers 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 150000004820 halides Chemical class 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract description 6
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000011592 zinc chloride Substances 0.000 abstract 2
- 235000005074 zinc chloride Nutrition 0.000 abstract 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- 101100058670 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) bsr gene Proteins 0.000 abstract 1
- 230000006583 body weight regulation Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a preparation method capable of regulating molecular weight for ultrahigh molecular weight polyethylene. The method of the present invention adopts compound titanium system catalysts which are prepared by a cogrinding-reaction method and have homogeneous particles and high activity and good molecular weight regulation effect. The main catalysts of the present invention are titanium compounds, accelerating agents are silicon compounds and ester, compound carriers are MgCl2 and ZnCl2, and cocatalysts are AlR3. The molecular weight of an ultrahigh molecular weight polyethylene product can be effectively regulated by controlling the content of catalyst components, namely that after the content of the titanium compounds as the components of the main catalysts is determined, the content of the ZnCl2 is regulated. When Zn/Ti (molar ratio) in the catalyst components is selected between 0.1 to 10, various specifications of the ultrahigh molecular weight polyethylene with the molecular weight of muw 60 to 610 ten thousand can be prepared, and the catalysis efficiency of the catalyst components is from 350 to 810 kgPE/gTi. The method of the present invention has the advantages of stable and easily controlled polymerization reaction, good particle size distribution of polymerisate, no caking, and less particle dust.
Description
The present invention relates to a kind of ultrahigh molecular weight polyethylene Preparation Method of regulating molecular weight.
As everyone knows, the performance of ultrahigh molecular weight polyethylene(UHMWPE) product is mainly determined by the molecular weight size of polymkeric substance, and adopt halogenide to be carried on the high activated catalyst that makes on the magnesium compound carrier by aluminum alkyls and a kind of titanium, can be used for preparing ultrahigh molecular weight polyethylene(UHMWPE) without the hydrogen accent, owing to can only control its molecular weight by polymerization technique, regulating effect is bad, and molecular weight is not easy to regulate on demand (plastics industry, 5,1 (1983); Polymer, 14 (8), 355 (1973)).
The purpose of this invention is to provide a kind of preparation method who regulates the ultrahigh molecular weight polyethylene(UHMWPE) of molecular weight.Adopt the method for regulating the component content in the catalyst system therefor, can regulate the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) product effectively on demand.
Preparation method of the present invention is as follows:
(1), the used catalyzer of polyreaction is composite Ti catalyst, its Primary Catalysts is a titanium compound, complex carrier is MgCl
2And ZnCl
2,, prepare as promotor with silicon compound and ester with following grindings-reaction method altogether:
1. with anhydrous MgCl
2, ZnCl
3, ester, silicon compound R °
nSiCl
4-a and titanium compound TiCl
4Or Ti (OR)
4, employing polishing altogether gets Powdered active matrix catalyzer (1), and its each component mole proportioning is: MgCl
2: ZnCl
2: TiCl
4=1: (0.007～0.489): (0.02～0.4), TiCl
4: Ti (OR)
4: R °
nSiCl
4-n=1: (0～0.25): (O.20～O.90), wherein R ° is C
1～C
8Alkyl or C
6H
5Base, a are 1～3 number, and R is the Bu base, by control ZnCl
2With the additional proportion of titanium compound, can prepare the ultrahigh molecular weight polyethylene(UHMWPE) of different molecular weight;
2. matrix catalysis (1) is dispersed in the alkanes solution, with alcohol moiety dissolving and reaction, used alkane is hexane, heptane, octane or decane, and alcohol adopts the various Fatty Alcohol(C12-C14 and C12-C18) of 1～8 carbon atom, and the consumption mol ratio is MgCl
2: alcohol=1: (0.1～3), 4～20ml alkane/gram base catalyst (1);
3. use AlR '
3-halide reagent or R "
2The Mg-halide reagent is handled the base catalyst (2) after pure processing reaction, obtains the suspension of catalyst solid component (2), used AlR '
3Middle R ' can be the alkyl that contains 2～8 carbon atoms, R "
2R among the Mg " is C
2H
5, C
4H
9, or C
6H
5Group, halide reagent are ZnCl
3, SiCl
4Or R ° of nSiCl
4-n, wherein R ° is C
1～C
3Alkyl or C
6H
5Base, n are 1～3 number, and the consumption mol ratio is alcohol: AlR '
3=1: (0.1～1), AlR '
3: halide reagent=1: (0.1～4);
4. adopt the examination of titanium compound-halogenation to handle the suspension of catalyst solid component (2), after filtration, wash, the suspension of catalyst solid component (3), wherein used titanium compound is TiCl
4, halide reagent is SiCl
4, the consumption mol ratio is TiCl
4: SiCl
4=1: (0.1～4), titanium compound: alcohol=(0.1～10): 1.
(2), polyreaction is with 120
#Gasoline or C
6～C
8Alkane is solvent, with aluminum alkyls AlR '
3Be promotor, its concentration is 0.3～3mmolAlR
3/ gasoline adopts the catalyzer that makes with aforesaid method, and its concentration is (1～12.5) * 10
-3Mmol Ti/L gasoline;
(3), polymeric reaction temperature is 60～85 ℃, pressure is 0.1～2MPa, the reaction times is 1～3 hour.
Used promotor AlEt preferably in the inventive method
3Or Al (i-Bu)
3
The composite Ti catalyst that adopts among the preparation method of the present invention is with the good MgCl of composite performance
2And ZnCl
3As complex carrier.After the content of Primary Catalysts composition titanium compound is determined, regulate ZnCl
3Content can control the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) product effectively, in catalyst preparation process,, use halide reagent ZnCl again through chemical reagent modifications such as alcohol
2, the reaction of titanium compound, silicon compound, make granules of catalyst evenly, short textureization and have high reactivity and good adjusting molecular weight effect; Zn/Ti in the control catalyst component (mol ratio) is 0.1～10, can prepare the ultrahigh molecular weight polyethylene(UHMWPE) that molecular weight is all size of Mw60～6,100,000, its catalytic efficiency is 350～810KgPE/gTi, stable polymerization reaction is easy to control, and the polymerisate size-grade distribution is good, nothing is lumpd, little particle dust.
The invention will be further described below by embodiment.
Embodiment one:
(1), cuing open of catalyzer is equipped with:
1. with anhydrous MgCl
340g, anhydrous ZnCl
30.3g (mol ratio Zn/Ti=0.1) places the vibro-grinding cylinder of clean anaerobic, exclusion, at N
2Protection was ground 4 hours down, added 2ml (C
6H
5)
2SiCl
2Ground 4 hours, and added the 2.2ml ethyl benzoate and ground 4 hours, add 0.75mlTi (OBn)
4Ground 4 hours, and added 2.2mlTiCl
4Ground 20 hours, at N
2The protection bottom discharge gets base catalyst (1).
2. in reaction flask, add heptane 40ml, base catalyst 10ml, constantly stirring dripped the 3.5ml dehydrated alcohol down in 30 minutes, heat temperature raising to 60～70 ℃ reaction 2 hours, cooling, stirring 2 hours.
3. under agitation, drip in 30 minutes and contain 20%AlEt
3AlEt
3-halide reagent 16.3ml (wherein Al/ halide reagent=3: 1).Be warming up to 70～80 ℃ of stirring reactions 4 hours, and be cooled to room temperature, get the suspension of catalyst solid component (2).
4. under agitation, titanium compound (the titaniferous mole number 6.25 * 10 of dropping 20% in 30 minutes
-3Mmol)-SiCl
4(content is 6.5 * 10
-3Mmol) n-heptane solution, be warming up to 80～90 ℃ of reactions 4 hours, filter, with the 40ml hexane wash, filter 5 times, add hexane 40ml, the suspension of catalyst solid component (3) is standby, can also be at N
2It is standby to protect vacuum-drying down to make catalyst solid.
(2), the preparation of ultrahigh molecular weight polyethylene(UHMWPE):
Adopt 2 liters of stills or 1 cubic metre of still to carry out ultrahigh molecular weight polyethylene and be equipped with, with 120
#Gasoline is made solvent, by 6.25 * 10
-3The concentration of mmol Ti/L gasoline adds the above-mentioned catalyzer that makes, and presses 1.75mmolAl (i-Bu)
3The concentration of/L gasoline adds promotor Al (i-Bu)
3, be that 65～75 ℃, pressure are reaction 2 hours under the 0.588MPa condition in temperature, catalytic efficiency is 810KgPE/gTi, molecular weight product Mw is 6,100,000.
Embodiment two to seven:
Zn/Ti, catalytic efficiency and molecular weight product are as shown in table 1 respectively in the polyreaction catalyst system therefor component, and other condition is identical with embodiment one with operation.
Shown in the table 1 be in embodiments of the invention one to the seven catalyst system therefor component, the weight-average molecular weight of Zn/Ti molar ratio, catalytic efficiency and product.As known from Table 1, prepare ultrahigh molecular weight polyethylene(UHMWPE),, just can regulate the molecular weight of product on demand as long as control the Zn/Ti molar ratio in the catalyst system therefor component by the inventive method.
Table 2 is when adopting method of the present invention to prepare ultrahigh molecular weight polyethylene(UHMWPE) with the catalyzer that adopts the polishing preparation, the size distribution of product and the contrast of catalytic efficiency.As can be known, the ultrahigh molecular weight polyethylene(UHMWPE) for preparing with method of the present invention has premium propertiess such as size distribution is narrow, nothing caking, few dust particle from table.
Fig. 1 is for preparing the polymerization kinetics curve of ultrahigh molecular weight polyethylene(UHMWPE) with the inventive method, it shows that polyreaction of the present invention has steady manageable advantage.
Claims (4)
1, a kind of preparation method who regulates the ultrahigh molecular weight polyethylene(UHMWPE) of molecular weight is characterized in that:
(1) the used catalyzer of polyreaction is a composite Ti catalyst, and its Primary Catalysts is a titanium compound, with MgCl
2And ZnCl
2As complex carrier, silicon compound and ester are as promotor, and its preparation method is as follows:
1. with anhydrous MgCl
2, ZnCl
2, silicon compound R ° nSiCl
4-n, ester and titanium compound TiCl
4Or Ti (OR)
4, adopting common polishing to make and have active base catalyst (1), the mol ratio of its each component proportioning is: MgCl
2: ZnCl
2: TiCl
4=1: (0.007～0.489): (0.02～0.4), TiCl
4: Ti (OR)
4: R ° of nSiCl
4-n=1: (0～0.25): (0.20～0.90), wherein R ° is C
1～C
8Alkyl or C
6H
5Base, n are 1～3 number, and R is the Bu base, by control ZnCl
2With the additional proportion of titanium compound, can prepare the ultrahigh molecular weight polyethylene(UHMWPE) of different molecular weight;
2. base catalyst (1) is dispersed in the alkane solution, with alcohol moiety dissolving and reaction, wherein alkane is hexane, heptane, octane or decane again, and alcohol adopts the various Fatty Alcohol(C12-C14 and C12-C18) of 1～8 carbon atom, and the consumption mol ratio is MgCl
2: alcohol (mol ratio)=1: (0.1～3), 4～20ml alkane/gram base catalyst (1);
3. use AlR '
3-halide reagent or R "
2The Mg-halide reagent is handled the base catalyst (1) after pure processing reaction, obtains the suspension of catalyst solid component (2); Used AlR '
3Middle R ' can be the alkyl that contains 2～8 carbon atoms, R "
2R among the Mg " is C
2H
5, C
4H
9Or C
6H
5Group, halide reagent are ZnCl
2, SiCl
4Or R ° of nSiCl
4-n, wherein R ° is C
1～C
8Alkyl or C
6H
5, n is 1～3 number, the consumption mol ratio is alcohol: Al=1: (0.1～1), Al: halide reagent=1: (0.1～4);
4. adopt titanium compound-halide reagent to handle the suspension of catalyst solid component (2), after filtration, wash the suspension of catalyst solid component (3), used titanium compound is TiCl
4, halide reagent is SiCl
4, TiCl in molar ratio
4: SiCl
4=1: (0.1～4), titanium compound: alcohol=(0.1～1 0): 1;
(2) with 120
#Gasoline or C
6～C
8Alkane is solvent, with aluminum alkyls AlR '
3Be promotor, catalyst concn is (1～12.5) * 10
-3MmolTi/L gasoline, cocatalyst concentration are 0.3～3mmol AlR '
3/ L gasoline;
(3) polymeric reaction temperature is 60～85 ℃, and pressure is 0.1～2MPa, 1～3 hour reaction times.
2, by the described Preparation Method of claim 1, it is characterized in that said ZnCl
2And the add-on of titanium compound is between 0.1～10 in the Za/Ti mol ratio, can prepare the ultrahigh molecular weight polyethylene(UHMWPE) of molecular weight Mw=60～6,100,000.
3, by the described preparation method of claim 1, it is characterized in that used promotor AlR '
3Be AlEt
3Or Al (i-Bn)
3
4, by the described preparation method of claim 1, it is characterized in that polymeric reaction temperature is 65～75 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93103156 CN1033703C (en) | 1993-03-23 | 1993-03-23 | Method capable of regulating molecular weight for preparing extra high molecular polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93103156 CN1033703C (en) | 1993-03-23 | 1993-03-23 | Method capable of regulating molecular weight for preparing extra high molecular polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076456A CN1076456A (en) | 1993-09-22 |
| CN1033703C true CN1033703C (en) | 1997-01-01 |
Family
ID=4984494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93103156 Expired - Fee Related CN1033703C (en) | 1993-03-23 | 1993-03-23 | Method capable of regulating molecular weight for preparing extra high molecular polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033703C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598512B2 (en) | 2012-10-22 | 2017-03-21 | China Petroleum & Chemical Corporation | Ultra-high molecular weight polyethylene resin and its application |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054137C (en) * | 1997-07-18 | 2000-07-05 | 中山大学 | Ethylene gaseous phase polymerization multifunction catalyst and its preparation method |
| US10731011B2 (en) * | 2017-12-07 | 2020-08-04 | Asahi Kasei Kabushiki Kaisha | Ultra-high molecular weight polyethylene powder and ultra-high molecular weight polyethylene fiber |
-
1993
- 1993-03-23 CN CN 93103156 patent/CN1033703C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598512B2 (en) | 2012-10-22 | 2017-03-21 | China Petroleum & Chemical Corporation | Ultra-high molecular weight polyethylene resin and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1076456A (en) | 1993-09-22 |
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