CN100413917C - Purifying method of carboxylates polyolefin enhancement nucleation agent - Google Patents
Purifying method of carboxylates polyolefin enhancement nucleation agent Download PDFInfo
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- CN100413917C CN100413917C CNB2005100887707A CN200510088770A CN100413917C CN 100413917 C CN100413917 C CN 100413917C CN B2005100887707 A CNB2005100887707 A CN B2005100887707A CN 200510088770 A CN200510088770 A CN 200510088770A CN 100413917 C CN100413917 C CN 100413917C
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Abstract
the invention discloses a purifying method of carboxylate polyolefin reinforced coring agent, which comprises the following steps: filtering; washing; adding solvent; adding 450-550wt% solvent from C1-3 lower alcohol or combined solvent from one or more lower alcohol of C5-6 naphthene, C6 aliphatic hydrocarbon; immersing at 30-80 deg.c for 2-6 deg.c; filtering the solvent; washing at 50-90 deg.c; filtering to obtain filter cake; displacing the residual solvent; drying for 7-8 h to obtain the product.
Description
Technical field
The present invention relates to method, adopt this method can effectively reduce the content of by product and reaction monomers in the carboxylates polyolefin nucleator, improve the purity of active principle, improve its effect the refining purifying of organic carboxylate class polyolefin nucleating agent.
Background technology
Adopt the method for adding nucleator, improve polyolefine, bending particularly, tensile property are important channels of polypropylene being carried out enhancing modified.Aromatic carboxylic acid metallic soap class is that a class has the nucleator that increases firm and transparent modified effect to polypropylene, and succeeded in developing by SHELL company the sixties in 20th century, and Application and Development is morning, but modified effect is limited.
" research of the crosslinked PE of ALUMINUM CARBOXYLIC salt active filler reinforcement " (" polymer material science and engineering " in July, 1989 of woods pleasant virtue, Yu Qiang etc., the fourth phase) synthetic method that provides is that the product with organic carboxyl acid and sodium hydroxide neutralization reaction is added to Aluminum Chloride Hexahydrate (ALCl
36H
2O) in the aqueous solution, replace/hydroxylating preparation aromatic carboxylic acid metallic soap class nucleator.Following two formulas of reaction formula:
General n is 1 or 2, and promptly the synthetic final product is monohydroxy salt, dihydroxyl salt, even does not have the mixture of hydroxy salt.Using this method can synthetic aroma family ALUMINUM CARBOXYLIC salt polyolefine enhancement nucleation agent, but applied research is found: monohydroxy aromatic carboxylic acid aluminium salt enhancing modified effect obviously is better than the dihydroxyl aromatic carboxylic acid aluminium salt (n=2) and the aromatic carboxylic acid aluminium salt of hydroxyl not.When adding not purification process, dihydroxyl salt and not having the higher crude product nucleator 0.3% of hydroxy salt content, the PP tensile yield strength is brought up to 37.0Mpa by 32.8Mpa, increase rate is less than 20%, Vicat softening point is brought up to 146 ℃ by 140 ℃, improve 6 ℃, bending elastic modulus is brought up to 1605Mpa by 1155Mpa, and increase rate is 39%.When adding after the same amount purification process high purity monohydroxy ALUMINUM CARBOXYLIC salt, the PP tensile yield strength is brought up to 40.5Mpa, and increase rate surpasses 23%, Vicat softening point is brought up to 156 ℃, improve 16 ℃, bending elastic modulus is brought up to 1722Mpa, and increase rate is 49%.Effect obviously is better than the crude product nucleator without purification process.In order to obtain with monohydroxy ALUMINUM CARBOXYLIC salt being the high purity aromatic carboxylic acids aluminium salt nucleator of benchmark, can adopt the method for the suitable reaction feed mol ratio of control, but still in final product, contain a spot of dihydroxyl salt, no hydroxy salt and reaction monomers unavoidably, causing with monohydroxy ALUMINUM CARBOXYLIC salt is the product purity reduction of benchmark, causes final effect to descend.Other improve with monohydroxy salt is the processing method of the product purity of benchmark, and not seeing has bibliographical information.
Summary of the invention
The objective of the invention is: a kind of polyolefine enhancement nucleation agent purification process is provided, use the content that this method can effectively reduce by product and reaction monomers in the carboxylates polyolefin nucleator, improve the purity of best active principle, improve the effect of carboxylates polyolefin nucleator.The contriver has carried out Related Experimental Study work, proposes the refining purification process of a kind of carboxylates polyolefin enhancement nucleation agent.
The purification process of a kind of carboxylates polyolefin enhancement nucleation agent of the present invention, its technological process be, gets crude carboxylic acid slurry aluminium salt nucleator, with water filtration, washing, removes the Na that reaction generates
+, Cl
-After washing gained filtrate pH value is 7.0～7.5, with solvent at 30～80 ℃ (preferably 40～60 ℃), preferably be with under the agitation condition, soaked the crude product nucleator 2～6 hours (if leave standstill, general soak time was controlled at 3～6 hours) after, with solvent filter, collect mother liquor. the filter cake that obtains with hot wash more than 50 ℃, filtration, the displacement residual solvent, drying obtained the finished product in 7～8 hours; Wherein solvent is C
1-3Lower alcohol, or use C
1-3In the time of lower alcohol, from C
5-6Naphthenic hydrocarbon, C
6The combination solvent of selecting one or more and lower alcohol to form in the aliphatic hydrocarbon; Weight in crude carboxylic acid slurry aluminium salt nucleator is 100%, and the add-on of solvent is: 450～550%.
Handle through above-mentioned purifying process, nucleator behind the purifying is cooked decomposition temperature, mass spectrum and infrared analysis, find the crude product nucleator of 240 ℃ of decomposition temperatures, decomposition temperature is brought up to more than 250 ℃, and infrared signature functional group and mass spectrum molecular weight show that main ingredient is the monohydroxy aromatic carboxylic-acid salts.The organic solvent mother liquor of collecting, be settled solution, after adding suitable quantity of water, the adularescent floss is separated out rapidly, collect this white flocculent substance, measure its decomposition temperature, locate out the peak at 200～220 ℃ and 100～120 ℃, mass spectrum and infrared analysis show that this white flocculent substance is mainly dihydroxyl salt and organic carboxyl acid monomer and the no hydroxy salt of trace.As calculated, before and after the purifying, nucleator weightlessness about 6% is benchmark with monohydroxy ALUMINUM CARBOXYLIC salt, and the crude product nucleator purity of purity about 90% is increased to more than 97%.Use and simultaneous test with nucleator behind the different refining pure metallization processes purifying, see embodiment.
Employed solvent is C among the present invention
1-3Lower alcohol or use C
1-3In the time of lower alcohol, from C
5-6Naphthenic hydrocarbon, C
6Select one or more and C in the aliphatic hydrocarbon
1-3The combination solvent that lower alcohol is formed, each component ratio of solvent is not particularly limited, but must contain lower alcohol, and lower alcohol is preferably in that shared weight is not less than 30% in the combination solvent.Use C separately
5-6Naphthenic hydrocarbon, C
6Other organic solvents such as aliphatic hydrocarbon or use aldehyde, ketone can cause refining purification effect not really desirable.C
1-3Lower alcohol can be methyl alcohol, ethanol, propyl alcohol, Virahol, propylene glycol, can be wherein one or more, C
5-6Naphthenic hydrocarbon, C
6Aliphatic hydrocarbon can be pentamethylene, hexanaphthene, hexane etc., can be wherein one or more, best solvent is the combination solvent that methyl alcohol or methyl alcohol and hexanaphthene combine.
Requirement will will be soaked 2～6 hours preferred 40～60 ℃ of soaking temperature with the crude carboxylic acid slurry aluminium salt nucleator after water filtration, the washing among the present invention under 30～80 ℃ of conditions with solvent.Soaking temperature is low excessively, a spot of dihydroxyl salt, organic carboxyl acid monomer and do not have hydroxy salt to dissolve dispersion effect in solvent poor in the nucleator, the directly refining purification effect of influence.The soaking temperature height can promote the dispersing and dissolving of a small amount of above-mentioned impurity component in solvent, helps refining purifying.But the temperature that is higher than 80 ℃ can cause a large amount of volatilizations of organic solvent, the closed unit that must be necessary.And generally obtained the comparatively refining purification effect of ideal at 60 ℃, taking all factors into consideration preferred soaking temperature is 40～60 ℃.Soak time is too short, can cause impurity component abundant dispersing and dissolving in solvent, leaves standstill therefore that soak time generally was not less than 3 hours under the situation, and soak time generally was not less than 2 hours under the subsidiary agitation condition.Operational cycle and purification effect are taken all factors into consideration, and soak time generally was controlled in 6 hours.
The filter cake that also requires among the present invention to obtain is replaced residual organic solvent, preferably 70 ℃～90 ℃ with the hot wash more than 50 ℃, filtration, particularly more than 80 ℃, temperature is crossed to hang down and can be caused residual minim organic solvent in the filter cake, produces smell, influences effect.。
Adopt purifying method of carboxylates polyolefin enhancement nucleation agent of the present invention, have following outstanding effect and characteristics:
(1), the crude carboxylic acid slurry salt nucleator purity of purity about 90% can be increased to more than 97%, and with the crude product nucleator of 240 ℃ of decomposition temperatures, decomposition temperature is brought up to more than 250 ℃ in monohydroxy ALUMINUM CARBOXYLIC salt.
(2) under addition is 0.3% situation, compare with the nucleator crude product, nucleator through purification process, polypropylene (PP) tensile yield strength increase rate brings up to 23% by 15%, the bending property increase rate is brought up to more than 48% by 39%, heat-drawn wire is brought up to more than 10 ℃ by about 6 ℃, and resistance to impact shock also has more significantly raising.
(3) the purification refine solvent is organic solvent commonly used, and purification refine technology is simple, easy to operate.The purification refine solvent reclaims and can repeatedly utilize through flash distillation.
Embodiment
Present embodiment, the product performance testing method that Comparative Examples adopted are:
Purifying weightlessness: constant weight method
Tensile property: GB/1040-92
Bending property: GB9341-88
Elongation at break: GB/1040-92
Vicat softening point: GB/T1633-2000
The acquisition of p t butylbenzoic acid salt nucleator crude product: self-control.The preparation method: with p t butylbenzoic acid add 20% sodium hydroxide molten in, stir under the room temperature, neutralization reaction 30～60min, neutralization reaction finishes, 30% liquor alumini chloridi is added reaction system, replace 40～60 ℃ of conditions/finish reaction behind hydroxylating 1～1.5hr, reaction product is filtered, drying grinds and obtains the nucleator crude product.Method is seen " research of the crosslinked PE of ALUMINUM CARBOXYLIC salt active filler reinforcement " (" polymer material science and engineering " in July, 1989, fourth phase) of Lin Mingde, Yu Qiang etc.
P t butylbenzoic acid salt nucleator crude product technical indicator: purity 91%, 238～242 ℃ of decomposition temperatures, bulk density 3.0g/cm
3, moisture content 1.0%.
PPF401: provider's Lanzhou Petrochemical Company petroleum chemical plant
Embodiment 1
Get p t butylbenzoic acid salt nucleator crude product 200 grams, use water filtration, washing, remove the Na+ that reaction generates, Cl-, after washing gained filtrate pH value is 7.0～7.5, use 1000ml methyl alcohol, be incubated 30 ℃, leave standstill and soak after 3 hours, under the same temperature condition of maintenance, methyl alcohol is filtered, collect mother liquor. with 50 ℃ of hot washes, the filter cake that filtration obtains, the displacement residual methanol, at 80 ℃, normal pressure obtained final sample down in dry 7～8 hours with the filter cake that obtains, metering, measure its decomposition temperature, addition 0.3% is that the polypropylene product of PPF401 (MFR2.4g/10min) is done application test to the Lanzhou Petrochemical Company petroleum chemical plant trade mark.Water is separated out by product and reaction monomers in the mother liquor, dry, metering.
Embodiment 2
Operation steps is with embodiment 1, and immersion, filtration temperature rise to 60 ℃, and with the filter cake that 90 ℃ of hot washes, filtration obtain, displacement residual methanol, other conditions are constant.
Embodiment 3
Form mixed solvent 1000ml at 1: 1 with methyl alcohol/hexanaphthene volumetric ratio, adopt 70 ℃ of hot washes, filter the filter cake that obtains, the displacement residual methanol, other operational conditions are with embodiment 1.
Embodiment 4
Form mixed solvent 1000ml with ethanol/hexane, wherein the shared weight percent of ethanol is 35%, and other operational conditions are with embodiment 1.
Embodiment 5
With methanol/ethanol/hexanaphthene/hexane volumetric ratio 1: 1: 1: 1 formed mixed solvent 1000ml, and other operational conditions are with embodiment 1.
Embodiment 6
With methyl alcohol/n-propyl alcohol/pentamethylene/hexane volumetric ratio 1: 1: 1: 1 formed mixed solvent 1000ml, and other operational conditions are with embodiment 1.
Embodiment 7
With methyl alcohol/propylene glycol/pentamethylene/hexane volumetric ratio 1: 1: 1: 1 formed mixed solvent 1000ml, and other operational conditions are with embodiment 1.
Embodiment 8
Operation steps is with embodiment 1, and immersion, filtration temperature rise to 65 ℃, and other conditions are constant.
Embodiment 9
Operation steps is with embodiment 1, and immersion (the subsidiary stirring), filtration temperature rise to 65 ℃.Soaked 2 hours, other conditions are constant.
Comparative Examples 1
Operation steps is with embodiment 1.Immersion (leaving standstill), filtration temperature are reduced to 25 ℃, and other conditions are constant.
Comparative Examples 2
Operation steps is with embodiment 1, and washing displacement hot water temperature becomes 40 ℃, and other conditions are constant.
Comparative Examples 3
Operation steps leaves standstill and soaked 1.5 hours with embodiment 1, and other conditions are constant.
Comparative Examples 4
With acetone 1000ml, other operations and test conditions are with embodiment 1.
Comparative Examples 5
Form mixed solvent 1000ml at 1: 1 with the ethanol/acetone volumetric ratio, other operational conditions are with embodiment 1.
Comparative Examples 6
Form mixed solvent 1000ml at 1: 1: 2 with methanol/ethanol/acetone volumetric ratio, other operational conditions are with embodiment 1.
Comparative Examples 7
Operation steps is with embodiment 1, and condition stirs and soaked 1.5 hours with embodiment 9, and other conditions are constant.
Comparative Examples 8
Form mixed solvent 1000ml with ethanol/hexane, wherein the ethanol weight percent is 25%, and other operational conditions are with embodiment 1.
The test-results of above embodiment and Comparative Examples is as shown in table 1 below.
Table 1
Annotate: 1. T
d/ ℃: nucleator crude product initial decomposition temperature, T
d'/℃: nucleator initial decomposition temperature behind the purifying.
2. Lanzhou petrochemical industry PPF401: 140 ℃ of Vicat softening points, tensile property 32.8Mpa, bending property 1155Mpa, elongation at break 650%.
By embodiment as seen, immersion, filtration temperature are lower than 30 ℃, and purification effect descends obviously, and immersion, filtration temperature raise, and are of value to purifying, but the consideration solvent volatility is not higher than 60 ℃ and is advisable.Soak time is less than 2 hours, and effect descends, and prolongs soak time, is of value to purifying, considers the operational cycle, and soak time is no more than 6 hours and is advisable.
Claims (6)
1. the purification process of an ALUMINUM CARBOXYLIC salt polyolefine enhancement nucleation agent is characterized in that crude carboxylic acid slurry aluminium salt nucleator, with water filtration, washing, removes the Na that reaction generates
+, Cl
-, after washing gained filtrate pH value is 7.0～7.5, under 30～80 ℃ of conditions, soak the crude product nucleator after 2～6 hours with solvent, with solvent filter, collect mother liquor. with the filter cake that hot wash more than 50 ℃, filtration obtain, displacement residual solvent, drying obtained the finished product in 7～8 hours; Wherein solvent is C
1～3Lower alcohol, or use C
1～3In the time of lower alcohol, from C
5～6Naphthenic hydrocarbon, C
6The combination solvent of selecting one or more and lower alcohol to form in the aliphatic hydrocarbon; Weight in crude carboxylic acid slurry aluminium salt nucleator is 100%, and the add-on of solvent is: 450～550%.
2. purification process according to claim 1 is characterized in that the temperature of solvent soaking crude carboxylic acid slurry aluminium salt nucleator is 40～60 ℃.
3. purification process according to claim 1 is characterized in that solvent is a methyl alcohol.
4. purification process according to claim 1 is characterized in that solvent is the combination solvent that methyl alcohol and hexanaphthene combine.
5. purification process according to claim 1, when it is characterized in that solvent is combination solvent, C
1～3Lower alcohol shared weight in combination solvent is not less than 30%.
6. purification process according to claim 1, it is characterized in that with behind the solvent filter with 70 ℃～90 ℃ hot washes, filter the filter cake obtain, displacement residual solvent.
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| CN104004253B (en) * | 2014-05-12 | 2016-09-14 | 漯河科莱堡洁具配件有限公司 | Heavy polymer nucleater modified super-high molecular weight polythene blending material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS627047A (en) * | 1985-07-04 | 1987-01-14 | Fuji Photo Film Co Ltd | Holder for cassette of photographic film |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS627047A (en) * | 1985-07-04 | 1987-01-14 | Fuji Photo Film Co Ltd | Holder for cassette of photographic film |
Non-Patent Citations (4)
| Title |
|---|
| 改善聚丙烯树脂性能用的成核剂评述. 翟羽伸.化工进展，第23卷第2期. 2004 |
| 改善聚丙烯树脂性能用的成核剂评述. 翟羽伸.化工进展，第23卷第2期. 2004 * |
| 透明成核剂及在聚丙烯中的应用. 赵芸芳，赵彦生，谢克昌.化学与粘合，第6期. 2003 |
| 透明成核剂及在聚丙烯中的应用. 赵芸芳，赵彦生，谢克昌.化学与粘合，第6期. 2003 * |
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