CN102199293A - Liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent, and preparation method thereof - Google Patents
Liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nucleating agent, and specifically relates to a liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent, and a preparation method thereof. The liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent comprises: polysiloxane as macromolecular scaffold, and mesogenic unit as side chain, wherein the mesogenic unit comprises flexible spacing unit, nucleus, and alkyl group or alkoxide group. The preparation method of the liquid-crystalline polysiloxane type [beta]-crystalline polypropylene nucleating agent comprises the following steps: synthesizing double-bond liquid-crystalline monomer; mixing hydrogen containing polymethylsiloxane with the liquid-crystalline monomer according to a molar ratio of 1:7 to 1:35; dissolving the mixture by 100 to 400ml of toluene or chloroform with 2 to 4ml of hexachloroplatinic acid as a catalyst, wherein the concentration of hexachloroplatinic acid is 5mg/ml, the reaction temperature is 65 DEG C, and the reaction time is 12 to 24 hours; after the reaction, adding the reactant into methanol; depositing, filtering, washing the resulting product 3 times with ethanol, and drying. With the above method, finish product is obtained.
Description
Technical field
The present invention relates to the nucleator technical field, be specifically related to a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator and preparation method thereof.
Background technology
Polypropylene (PP) has that relative density is low, nontoxic, heat-resisting, corrosion-resistant, electrical insulating property is good, easily processing and advantage such as inexpensive, become the fastest, the most active kind of new varieties of rate of growth in the five big general synthetic resins, be used widely in fields such as chemical industry, light industry and household electrical appliances.PP is a kind of hemicrystalline polymer, presents
α,
β,
γ,
δWith intend 5 kinds of forms of hexahedron, wherein with
αBrilliant with
βCrystalline substance is more common, and its crystalline texture and form directly influence the final physical and mechanical property of PP material.
Usually, the commercialization polypropylene presents
αCrystal formation,
αCrystal polypropylene (
α-PP) have a good comprehensive performances, but its low-temperature impact resistance is relatively poor relatively.With
α-PP compares,
βCrystal polypropylene (
β-PP) impact has sorption preferably, and its notched Izod impact strength and heat-drawn wire have raising by a relatively large margin, can be widely used in fields such as trolley part, tubing system, microporous fibre and films.Utilize its good toughness, can prepare the high-impact goods, as bumper, battery container, hot-water line etc.; In addition, utilize
βThe compactness extent of-PP is relatively low, and non-crystalline region is easy to be drawn back the characteristics that form little crazing or microcavities, and microporous fibre, strainer reach easily stain oil type PP capactive film preferably with many microporous breathable films, water-absorbent to make gaseous interchange.
With among the PP
αIt is brilliant different,
βCrystalline substance is metastable on thermodynamics, on the kinetics is to be unfavorable for a kind of crystal formation of generating, is difficult to obtain and keep under common processing or crystallization condition.At present, add
βBrilliant nucleator is induced stable in PP
βCrystalline substance is preparation
βThe valid approach of-PP.So far, bibliographical information
βBrilliant nucleator mainly contains four classes: 1. some has the condensed ring compounds of directrix plane structure, stings ketone, triphen dithiazine etc. as the brilliant quinoline a word used for translation of γ, and shortcoming is easily to make product painted; 2. some salt of IIA family metallic element and the mixture of di-carboxylic acid, as mixture of pimelic acid and calcium stearate etc., shortcoming is the poor heat resistance of such nucleator; 3. amides nucleator, as 2,6-phthalic acid Cyclohexamide, 2,6-naphthalic acid Cyclohexamide etc.; 4. rare earth class nucleator, some rare earth compounds such as lanthanum carbide etc.Above-mentioned these
βBrilliant nucleator all is a micromolecular compound, although these small molecules
βBrilliant nucleator has nucleation efficient height, and some have obtained to use, but they also exist " agglomeration is strong ", " dispersed bad " and problems such as " easily separating out " from the PP matrix in PP.
Summary of the invention
The objective of the invention is the deficiency at the prior art existence, a kind of macromole liquid crystalline polysiloxane class beta-crystal polypropylene nucleator and preparation method thereof is provided, the beta-crystal polypropylene nucleator performance that obtains is stable more, efficient.
Liquid crystalline polysiloxane class beta-crystal polypropylene nucleator of the present invention, as macromolecular skeleton, as side chain, liquid crystal unit comprises flexible spacer, liquid crystal nuclear and alkyl or alkoxyl group with liquid crystal unit with polysiloxane chain, the general structure of nucleator is (a),
Liquid crystal nuclear in the described liquid crystal unit is phenyl ester biphenyl (b) or phenyl ester phenyl ester benzene (c) or phenyl ester biphenyl ester benzene (d), and molecular formula is respectively:
Alkyl in the described liquid crystal unit is methyl or ethyl or amyl group, and alkoxyl group is a methoxy or ethoxy;
The preparation method of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator of the present invention may further comprise the steps: at first synthetic double bond containing liquid crystal monomer; After will gathering the methyl hydrogen-containing siloxane then 1:7 ~ 1:35 mixing in molar ratio with liquid crystal monomer, with 100 ~ 400ml toluene or chloroform dissolving, in temperature is under 65 ℃ of conditions, with 2 ~ 4ml concentration is that the chlordene of 5mg/ml closes platinic acid as catalyzer, behind reaction 12 ~ 24h, reactant is poured into precipitation in the methyl alcohol, filtered, use 3 after drying of washing with alcohol again, obtain the finished product;
Described double bond containing liquid crystal monomer be 4-ethoxybenzoic acid-4 '-undecylenic acid to xenol dibasic acid esters or 4-ethyl benzoate-4 '-allyloxy phenylformic acid Resorcinol dibasic acid esters or 4-amylbenzene formic acid-4 '-hendecene acyloxy phenylformic acid is to the xenol dibasic acid esters.
Compared with prior art, characteristics of the present invention and beneficial effect thereof are:
1. the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator that has good dispersion and consistency with polypropylene of the present invention preparation, utilization be in " liquid crystal state " easily bioactive molecule of orientation provide a large amount of nucleation sites for the arrangement of polypropylene chains, played the effect of heterogeneous nucleation, both accelerated polyacrylic crystallization velocity, also reduced the size of spherocrystal, and spherolite is more evenly distributed;
2. the ordered arrangement of the liquid crystal unit in the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator of the present invention's preparation provides orderly interface for crystalling propylene, reduced the free energy barrier potential of nucleation, improved the axial ordered arrangement of C of polypropylene chains, induced that stable, high-load β is brilliant to be generated;
3. Fig. 1 is according to the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator of the present invention of the polarized light microscope observing preparation deployment conditions at PP, as seen the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator of the present invention's preparation has good consistency with dispersed in polypropylene, overcome the brilliant nucleator of low molecule β and in PP, had " agglomeration is strong ", " dispersed bad " and problems such as " easily from the PP matrix, separating out ", the stability and the polyacrylic life-span of nucleation of having improved nucleation with consistency;
4. processing step of the present invention is simple and easy to do, need not expensive equipment and harsh working condition.
Description of drawings
Fig. 1 a is the dispersion effect figure of nucleator of the present invention in polypropylene in the blend sample 2, and Fig. 1 b is the dispersion effect figure of nucleator of the present invention in polypropylene in the blend sample 3;
Fig. 2 is the WAXD curve after the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator that adding blend sample 2 prepares in polypropylene.
Embodiment
Below in conjunction with embodiment the present invention is elaborated, but protection scope of the present invention is not limited only to following liquid crystalline polysiloxane class beta-crystal polypropylene nucleator embodiment:
Embodiment 1:
At first synthetic double bond containing liquid crystal monomer 4-ethoxybenzoic acid-4 '-undecylenic acid is to the xenol dibasic acid esters, comprises 2 steps:
(1) in the 1000mL there-necked flask, adds 150.0g to xenol, 400mL tetrahydrofuran (THF) and 20mL pyridine, and drip 3 DMF hydrotropies, after the stirring at normal temperature dissolving, slowly drip the 0.2mol ethoxy benzoyl chloride, back flow reaction 8h, screw out an amount of solvent after, residual solution is poured in the big water gaging, obtain white solid, remove xenol with 0.5% NaOH solution washing, adjust pH is washed 3 ~ 5 times with ethanolic soln to neutral again, obtain product with acetone recrystallization, obtain liquid crystal 4-ethoxybenzoic acid-4 '-xenol, its fusing point is 217 ℃, productive rate: 40%;
(2) in the 100mL there-necked flask, add 6.4g 4-ethoxybenzoic acid-4 '-xenol, the 25mL trichloromethane, the 2mL pyridine, stirring and dissolving slowly drips 4.5mL 4-hendecene acyl chlorides, back flow reaction 10h, reaction solution is poured in the methyl alcohol, obtained precipitation, filter, use ethyl alcohol recrystallization again, obtain liquid crystal monomer 4-ethoxybenzoic acid-4 '-undecylenic acid is to the xenol dibasic acid esters, fusing point is 85 ℃; Productive rate: 66%;
To gather then methyl hydrogen-containing siloxane (PMHS) and liquid crystal monomer 4-ethoxybenzoic acid-4 '-undecylenic acid feeds intake for 1:35 in molar ratio to xenol dibasic acid esters monomer; be dissolved in the 100mL toluene; under nitrogen protection, be warming up to 65 ℃; adding concentration is that the chlordene of 5mg/ml closes platinic acid catalyzer 4mL; reaction 24h; with infrared spectrometer reaction process is monitored, observe Si H key among the PMHS at 2166cm
-1The stretching vibration peak completely dissolve, illustrate that all Si H react with liquid crystal unit, this polyreaction is thoroughly finished, then reactant is poured in the methyl alcohol and precipitated, filter, reusable heat washing with alcohol 3 times, vacuum-drying promptly obtain the finished product liquid crystalline polysiloxane class beta-crystal polypropylene nucleator, and its structural formula is as follows:
Embodiment 2:
At first synthetic double bond containing liquid crystal monomer 4-ethyl benzoate-4 '-allyloxy phenylformic acid Resorcinol dibasic acid esters, comprise 5 steps:
(1) the 50.0g ethyl benzoate is added in the 250mL there-necked flask, add 50mLSOCl
2, 4 DMF, stirring and dissolving, normal-temperature reaction 5h, reflux 2h, remaining SOCl is removed in underpressure distillation then
2, obtain light yellow transparent liquid, be the ethylamino benzonitrile acyl chlorides, productive rate: 99%;
(2) in the 500mL there-necked flask, add the 183g Resorcinol, add 220mL THF and 25mL pyridine again and make it dissolving, stir the THF solution 40mL that slowly drips above-mentioned ethylamino benzonitrile acyl chlorides down fast, react 2h under the room temperature, back flow reaction 8h, after the cooling, steam most THF in the solution, concentrated solution is poured in the beaker that fills big water gaging, precipitation, filter hot water wash several times, ethyl alcohol recrystallization, white solid 4-ethyl benzoate-4 '-hydroxybenzene, fusing point is 136 ℃; Productive rate: 62%;
(3) in the there-necked flask of 1000mL, add the 138g P-hydroxybenzoic acid in, 400mL ethanol stirs, dissolving drips the 150mL aqueous solution that contains 120g potassium hydroxide and 0.5g potassiumiodide, drips 80mL 3-bromopropylene again, back flow reaction 24h.Reaction solution is poured in the beaker of 2000mL, acidifying, regulating the pH value is 3 ~ 4, and suction filtration behind hot water repetitive scrubbing several times, filters, and ethyl alcohol recrystallization gets 4-allyloxy phenylformic acid.Fusing point: 164 ℃; Productive rate: 70%;
(4) in the there-necked flask of 100mL, add 3.5g allyloxy phenylformic acid and 20mL thionyl chloride (SOCl
2), 3 DMF, stirring at normal temperature reaction 5h is warming up to 60 ℃ of reaction 2h then, and reaction finishes the back underpressure distillation and removes excessive SOCl
2, obtain light yellow transparent liquid 4-allyloxy Benzoyl chloride, productive rate: 99%;
(5) with 5.2g 4-ethyl benzoate-4 '-hydroxybenzene is dissolved in the trichloromethane and 2mL pyridine of 30mL, dissolving, drip the chloroform soln 10mL of above-mentioned 4-allyloxy Benzoyl chloride under the stirring at normal temperature, normal-temperature reaction 2h, back flow reaction 16h, reaction solution is poured in the beaker that fills methyl alcohol, precipitation is filtered ethyl alcohol recrystallization, faint yellow solid, be liquid crystal monomer 4-ethyl benzoate-4 '-allyloxy phenylformic acid Resorcinol dibasic acid esters.Fusing point: 136 ℃; Productive rate: 70%;
To gather then methyl hydrogen-containing siloxane and 4-ethyl benzoate-4 '-allyloxy phenylformic acid Resorcinol dibasic acid esters monomer is dissolved in the 100mL toluene for 1:7 in molar ratio; under nitrogen protection, be warming up to 65 ℃; adding concentration is that the chlordene of 5mg/ml closes platinic acid catalyzer 2mL; reaction 15h; with infrared spectrometer reaction process is monitored, observe Si H key among the PMHS at 2166cm
-1The stretching vibration peak completely dissolve, illustrate that all Si H react with liquid crystal unit, this polyreaction is thoroughly finished, reactant poured in the methyl alcohol precipitate, filter, reusable heat washing with alcohol 3 times, vacuum-drying promptly obtain the finished product liquid crystalline polysiloxane class beta-crystal polypropylene nucleator, and its structural formula is as follows:
The clearing point of the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator that adopts in the present embodiment is 195 ℃, and the temperature of the crystal habit completely dissolve of PP is 171 ℃, therefore select 180 ℃ temperature to get off to inquire into the dispersion effect of this nucleator in PP, polarized light microscope observing shows, it for the content of this nucleator 0.4% blend sample, because the relative content of nucleator is few, and in the time of 180 ℃, can't see fairly obvious liquid crystal property or texture, see Fig. 1 (a), when the content of this nucleator is 2.0%, can observe its liquid crystal property, see Fig. 1 (b), because under 180 ℃ of temperature, PP melts fully, and residual form is liquid crystal texture, and mesomorphic distribution shows that the dispersion of this nucleator in PP is more uniform among the figure
Fig. 2 is the WAXD curve after the liquid crystalline polysiloxane class beta-crystal polypropylene nucleator that adding blend sample 2 prepares in polypropylene, as seen from the figure, the brilliant characteristic diffraction peak of tangible typical β has appearred near 2 θ are 16.0 °, and a little less than the diffraction peak of α crystalline substance becomes quite, show that this nucleator is the brilliant nucleator of a kind of novel efficient β;
Embodiment 3:
At first synthetic double bond containing liquid crystal monomer 4-amylbenzene formic acid-4 '-hendecene acyloxy phenylformic acid is to the xenol dibasic acid esters, comprises 5 steps:
(1) in the there-necked flask of 1000mL, add the 138g P-hydroxybenzoic acid in, 400mL ethanol stirs, dissolving drips the 150mL aqueous solution that contains 120g potassium hydroxide and 0.5g potassiumiodide, drips 60mL11-bromine hendecene again, back flow reaction 24h.Reaction solution is poured in the beaker of 2000mL, acidifying, regulating the pH value is 3 ~ 4, and suction filtration behind hot water repetitive scrubbing several times, filters, and ethyl alcohol recrystallization gets 4-hendecene aminobenzoic acid.Productive rate: 63%;
(2) in the 100mL there-necked flask, add 19.2g amylbenzene formic acid respectively, 60mL thionyl chloride, 4 DMF, stirring and dissolving, normal-temperature reaction 5h, heating reflux reaction 3h.Excessive thionyl chloride is removed in underpressure distillation then, gets the amylbenzene formyl chloride.Productive rate: 99%;
(3) in the 1000ml there-necked flask, add 150g respectively to xenol, the 400mL tetrahydrofuran (THF), the 20mL pyridine, stirring and dissolving slowly drips the tetrahydrofuran solution of amylbenzene formyl chloride, normal-temperature reaction 2h, heating reflux reaction 8h then under stirring fast.Rotary evaporation goes out most of solvent, and concentrated solution is poured in the big water gaging, filter white solid, remove remainingly to xenol with 1.5% NaOH solution washing, adjust pH is to neutral, again with ethyl alcohol recrystallization obtain 4-amylbenzene formic acid-4 '-xenol.Fusing point: 173 ℃; Productive rate: 36%;
(4) in the 100mL there-necked flask, add 14g 4-hendecene aminobenzoic acid respectively, the 50mL thionyl chloride, 3 DMF, normal-temperature reaction 6h is heated to 60 ℃ of back flow reaction 2h.Excessive thionyl chloride is removed in underpressure distillation, gets 4-hendecene acyloxy Benzoyl chloride, productive rate 96%;
(5) in the 250mL there-necked flask, add respectively 18g 4-amylbenzene formic acid-4 '-xenol, the 150mL trichloromethane, the 10mL pyridine, stirring and dissolving, the chloroform soln 10mL of the 4-hendecene oxygen base Benzoyl chloride of preparation more than slowly dripping under stirring fast, normal-temperature reaction 2h is heated to 60 ℃ of back flow reaction 24h.Rotary evaporation goes out most of solvent, and concentrated solution is poured in the methyl alcohol, and precipitation is filtered, and uses ethyl alcohol recrystallization again, liquid crystal monomer 4-amylbenzene formic acid-4 '-hendecene acyloxy phenylformic acid is to the xenol dibasic acid esters.Fusing point: 152 ℃; Productive rate: 78%;
To gather then methyl hydrogen-containing siloxane (PMHS) and liquid crystal monomer 4-amylbenzene formic acid-4 '-hendecene acyloxy phenylformic acid feeds intake for 1:35 in molar ratio to the xenol dibasic acid esters; be dissolved in the 100mL trichloromethane; under nitrogen protection, be warming up to 65 ℃; adding concentration is that the chlordene of 5mg/ml closes platinic acid catalyzer 4mL; reaction 24h; with infrared spectrometer reaction process is monitored, observe Si H key among the PMHS at 2166cm
-1The stretching vibration peak completely dissolve, illustrate that all Si H react with liquid crystal unit, this polyreaction is thoroughly finished, then reactant is poured in the methyl alcohol and precipitated, filter, reusable heat washing with alcohol 3 times, vacuum-drying promptly arrive the finished product liquid crystalline polysiloxane class beta-crystal polypropylene nucleator, and its structural formula is as follows:
Liquid crystalline polysiloxane class beta-crystal polypropylene nucleator and PP blend:
With above-mentioned liquid crystalline polysiloxane class beta-crystal polypropylene nucleator and polypropylene by different quality than thorough mixing after, pour in the Banbury mixer mould, at 180 ℃ of following banburying 15min, rotating speed 60 r/min, obtain the blend sample, the relative content of the β crystalline substance that calculates according to the X-ray diffraction peak sees Table 1
| Routine number of the brilliant nucleator blend of polypropylene/liquid crystalline polysiloxane class β | The brilliant nucleator (mass ratio) of polypropylene/liquid crystalline polysiloxane class β | The β crystalline phase is to content (%) |
| The contrast sample | 100:0 | 0 |
| Blend sample 1 | 100:0.2 | 66 |
| Blend sample 2 | 100:0.4 | 87 |
| Blend sample 3 | 100:0.6 | 71 |
| Blend sample 4 | 100:1.0 | 68 |
| Blend sample 5 | 100:2.0 | 65 |
As seen beta-crystal polypropylene nucleating effect of the present invention is fine, accounts for polypropylene mass ratio 2% when following in the nucleator quality that adds, and the beta-crystal polypropylene ratio that obtains is more than 65%, and wherein during nucleator massfraction 0.4%, the β crystalline phase that obtains is 87% to content.
Claims (6)
1. liquid crystalline polysiloxane class beta-crystal polypropylene nucleator, it is characterized in that its with polysiloxane chain as macromolecular skeleton, as side chain, liquid crystal unit comprises flexible spacer, liquid crystal nuclear and alkyl or alkoxyl group with liquid crystal unit, the general structure of this nucleator is (a)
2. a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator according to claim 1 is characterized in that liquid crystal nuclear is phenyl ester biphenyl (b) or phenyl ester phenyl ester benzene (c) or phenyl ester phenyl ester biphenyl (d) in the liquid crystal unit, and molecular formula is respectively:
。
3. a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator according to claim 1 is characterized in that the alkyl in the described liquid crystal unit is methyl or ethyl or amyl group, and alkoxyl group is a methoxy or ethoxy.
4. the preparation method of a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator according to claim 1 is characterized in that may further comprise the steps: at first synthetic double bond containing liquid crystal monomer; After will gathering the methyl hydrogen-containing siloxane then 1:7 ~ 1:35 mixing in molar ratio with liquid crystal monomer, with 100 ~ 400ml dissolution with solvents, in temperature is under 65 ℃ of conditions, with 2 ~ 4ml concentration is that the chlordene of 5mg/ml closes platinic acid as catalyzer, behind reaction 12 ~ 24h, reactant is poured into precipitation in the methyl alcohol, filtered, use 3 after drying of washing with alcohol again, obtain the finished product.
5. the preparation method of a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator according to claim 4, it is characterized in that described double bond containing liquid crystal monomer be 4-ethoxybenzoic acid-4 '-undecylenic acid to xenol dibasic acid esters or 4-ethyl benzoate-4 '-allyloxy phenylformic acid Resorcinol dibasic acid esters or 4-amylbenzene formic acid-4 '-hendecene acyloxy phenylformic acid is to the xenol dibasic acid esters.
6. the preparation method of a kind of liquid crystalline polysiloxane class beta-crystal polypropylene nucleator according to claim 4 is characterized in that described solvent is toluene or chloroform.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571057A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Modified polypropylene composition and preparation method thereof |
| CN106397987A (en) * | 2016-11-01 | 2017-02-15 | 常州大学 | PP(polypropylene)/liquid crystal polymer composite with high beta-form crystal content and preparation method |
| CN109206808A (en) * | 2018-10-31 | 2019-01-15 | 西安科技大学 | A kind of preparation method of heat-conducting polymer dispersed liquid crystal film |
| CN110483935A (en) * | 2019-09-19 | 2019-11-22 | 杭州聚丰新材料有限公司 | A kind of polypropylene macromolecular reinforcement nucleating agent and the preparation method and application thereof |
-
2011
- 2011-03-25 CN CN 201110072389 patent/CN102199293A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《高分子学报》 20100920 胡建设等 向列相液晶共聚物作为beta晶成核剂对等规聚丙烯结晶结构与热性能的影响 第1100-1107页 1-6 , 第9期 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571057A (en) * | 2013-11-06 | 2014-02-12 | 江南大学 | Modified polypropylene composition and preparation method thereof |
| CN103571057B (en) * | 2013-11-06 | 2016-03-30 | 江南大学 | A kind of modified poly propylene composition and preparation method thereof |
| CN106397987A (en) * | 2016-11-01 | 2017-02-15 | 常州大学 | PP(polypropylene)/liquid crystal polymer composite with high beta-form crystal content and preparation method |
| CN106397987B (en) * | 2016-11-01 | 2019-03-22 | 常州大学 | Polypropylene/the liquid crystal polymer composite and preparation method of high-beta crystal content |
| CN109206808A (en) * | 2018-10-31 | 2019-01-15 | 西安科技大学 | A kind of preparation method of heat-conducting polymer dispersed liquid crystal film |
| CN109206808B (en) * | 2018-10-31 | 2021-06-08 | 西安科技大学 | Preparation method of heat-conducting polymer liquid crystal dispersion film |
| CN110483935A (en) * | 2019-09-19 | 2019-11-22 | 杭州聚丰新材料有限公司 | A kind of polypropylene macromolecular reinforcement nucleating agent and the preparation method and application thereof |
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Application publication date: 20110928 |