CN102153687B - Liquid-crystal poly(methyl)acrylate beta-crystal-form polypropylene nucleating agent and preparation method thereof - Google Patents
Liquid-crystal poly(methyl)acrylate beta-crystal-form polypropylene nucleating agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nucleating agents, and particularly relates to a liquid-crystal poly(methyl)acrylate beta-crystal-form polypropylene nucleating agent and a preparation method thereof. The liquid-crystal poly(methyl)acrylate beta-crystal-form polypropylene nucleating agent provided by the invention uses a poly(methyl)acrylate chain as the macromolecule frame, and uses a mesogenic unit as a side chain, wherein the mesogenic unit comprises a flexible space group, a liquid-crystal nucleus, and an alkyl or alkoxy group. The preparation method of the liquid-crystal poly(methyl)acrylate beta-crystal-form polypropylene nucleating agent comprises the following steps: synthesizing a double-bond-containing liquid-crystal monomer; dissolving 2-5g of the liquid-crystal monomer in 50-100 ml of solvent, and adding 0.02-0.005g of azodiisobutyronitrile at 60 DEG C to react for 12-24 hours; and pouring the reactant in methanol, precipitating, filtering, washing with ethanol three times, and drying to obtain the final product.
Description
Technical field
The present invention relates to the nucleator technical field, be specifically related to poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of a kind of liquid crystal 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, makes the many microporous breathable films of gaseous interchange, water-absorbent microporous fibre, strainer and easy stain oil type PP capactive film preferably.
With among the PP
αIt is brilliant different,
βBrilliant is metastable at 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 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 is as 2,6-phthalic acid Cyclohexamide etc.; 4. rare earth class nucleator is as lanthanum carbide etc.Above-mentioned these
βBrilliant nucleator all is micromolecular compound, although these small molecules
βBrilliant nucleator has nucleation efficient height, and some have obtained to use, but they also exist in PP such as " agglomeration is strong ", " dispersed bad " and problems such as " easily separating out from the PP matrix ".
Summary of the invention
The objective of the invention is the deficiency at the prior art existence, poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of a kind of macromole liquid crystal and preparation method thereof is provided, obtained a kind of novel beta-crystal polypropylene nucleator.
Liquid crystal of the present invention gathers (methyl) esters of acrylic acid beta-crystal polypropylene nucleator, 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 poly-(methyl) acrylate chains, the general structure of nucleator is (a)
Liquid crystal nuclear in the described liquid crystal unit is phenyl ester phenyl ester benzene (b) or phenyl ester phenyl ester biphenyl (c) or phenyl ester biphenyl (d), and molecular formula is respectively:
；
Alkyl in the described liquid crystal unit is methyl or ethyl or amyl group, alkoxyl group be methoxy or ethoxy or heptan the oxygen base;
The preparation method of poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of liquid crystal of the present invention may further comprise the steps: at first synthetic double bond containing liquid crystal monomer; Then with 2 ~ 5g liquid crystal monomer with 50 ~ 100ml dissolution with solvents, be under 60 ℃ of conditions in temperature, add the Diisopropyl azodicarboxylate catalyzer of 0.02 ~ 0.005g, behind reaction 12 ~ 24h, reactant is poured in the methyl alcohol into precipitation, filtered, use after the washing with alcohol 3 times dryly again, obtain the finished product;
Described double bond containing liquid crystal monomer be 4-ethoxybenzoic acid-4 '-acryloxy (oxyethyl group) phenylformic acid Resorcinol dibasic acid esters or 4-amylbenzene formic acid-4 '-acryloxy (ω-hexyloxy) phenylformic acid to xenol dibasic acid esters or 4-oxygen in heptan base biphenyl-4 '-methacryloxy (oxyethyl group) benzoic ether.
Compared with prior art, characteristics of the present invention and beneficial effect thereof are:
1. the liquid crystal that has good dispersion and a consistency with polypropylene of the present invention preparation gathers (methyl) esters of acrylic acid beta-crystal polypropylene nucleator, 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 poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the liquid crystal of the present invention's preparation provides orderly interface for crystalling propylene, reduced the free energy barrier potential of nucleation, improve the axial ordered arrangement of C of polypropylene chains, induced the brilliant generation of β stable, high-content;
3. Fig. 1 is according to the deployment conditions of poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the liquid crystal of the present invention of polarized light microscope observing preparation at PP, as seen poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the liquid crystal 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 ", stability and the polyacrylic life-span of nucleation of having improved nucleation;
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 (content is 0.2%) in polypropylene, and Fig. 1 b is the dispersion effect figure of nucleator of the present invention (content is 2%) in polypropylene;
Fig. 2 is the WAXD curve after the liquid crystal of adding blend sample 3 preparations in polypropylene gathers (methyl) esters of acrylic acid beta-crystal polypropylene nucleator.
Embodiment
Elaborate below in conjunction with the present invention of embodiment, but protection scope of the present invention is not limited only to poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator embodiment of following liquid crystal:
Embodiment 1:
At first synthetic double bond containing liquid crystal monomer 4-ethoxybenzoic acid-4 '-acryloxy (oxyethyl group) phenylformic acid Resorcinol dibasic acid esters, comprise 4 steps:
(1) take by weighing the 13.8g P-hydroxybenzoic acid in the there-necked flask of 100mL, add 25mL ethanol, stir, dissolving slowly drips the 25mL aqueous solution that contains 12g potassium hydroxide and 0.1g potassiumiodide, drips the 6.6mL ethylene chlorhydrin again, back flow reaction 15h.After the cooling, reaction solution is poured in the beaker of 200mL, 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-hydroxy ethoxy phenylformic acid.Fusing point: 179 ℃; Productive rate: 61%;
(2) take by weighing 5.6g 4-hydroxy ethoxy phenylformic acid, a small amount of MEHQ in the there-necked flask of 100mL, add 60mL vinylformic acid, stir, dissolve, slowly drip the vitriol oil of 0.3mL 98%, heating reflux reaction 24h.After the cooling, reaction solution is poured in the beaker of 200mL, washing, precipitation is filtered, and behind the reusable heat water repetitive scrubbing several times, ethyl alcohol recrystallization gets 4-acryloxy ethoxybenzoic acid.Fusing point: 138 ℃; Productive rate: 60%;
(3) in the 100mL there-necked flask, add the 10g Resorcinol, add 18mL THF and 1.5mL pyridine again and make it dissolving, stir the THF solution 5mL that slowly drips the 0.03mol ethoxy benzoyl chloride down fast, react 4h under the room temperature, back flow reaction 6h.After the cooling, steam most solvents, concentrated solution is poured in the beaker that fills big water gaging, precipitation is filtered, the hot water wash several times, ethyl alcohol recrystallization, get 4-ethoxybenzoic acid-4 '-hydroxybenzene.Fusing point: 168 ℃; Productive rate: 70%;
(4) in the 100mL there-necked flask, take by weighing 5.9g 4-acryloxy ethoxybenzoic acid, 5.5g N, N '-dicyclohexylcarbodiimide (DCC) and 0.5g 4-Dimethylamino pyridine (DMAP) are dissolved in the methylene dichloride of 25mL stirring and dissolving.Stir slowly drip down the 4-ethoxybenzoic acid-4 that is dissolved with 6.4g '-the dichloromethane solution 15mL of hydroxybenzene, normal-temperature reaction 2h, back flow reaction 24h.After the cooling, add the 25mL deionized water, behind the stirring 0.5h, filter and get filtrate.Mix with filtrate with dilute hydrochloric acid, 5% sodium carbonate solution respectively, standing demix takes off a layer solution.After steaming most solvents, separate out with methanol extraction, filter, ethyl alcohol recrystallization gets white powder.Be liquid crystal monomer 4-ethoxybenzoic acid-4 '-acryloxy (oxyethyl group) phenylformic acid Resorcinol dibasic acid esters.Fusing point: 131 ℃; Productive rate: 57%;
Get then 2g liquid crystal monomer 4-ethoxybenzoic acid-4 '-acryloxy (oxyethyl group) phenylformic acid Resorcinol dibasic acid esters; be dissolved in wiring solution-forming in the 20mL tetrahydrofuran (THF); the 50mL flask that injection vacuumizes; under nitrogen protection, be warming up to 60 ℃; the Diisopropyl azodicarboxylate catalyzer that adds 0.02g; reaction 24h monitors reaction process with infrared spectrometer, observes two keys in the monomer at 1642cm
-1About the stretching vibration peak completely dissolve, illustrate that this polyreaction thoroughly finishes, reactant is poured in the methyl alcohol precipitated then, filter, reusable heat washing with alcohol 3 times, vacuum-drying namely obtain poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the finished product liquid crystal, and its structural formula is as follows:
。
Embodiment 2:
At first synthetic double bond containing liquid crystal monomer 4-amylbenzene formic acid-4 '-acryloxy (ω-hexyloxy) phenylformic acid is to the xenol dibasic acid esters, comprises 4 steps:
(1) take by weighing the 16.5g P-hydroxybenzoic acid in the there-necked flask of 100mL, add 30mL ethanol, stir, dissolving slowly drips the 25mL aqueous solution that contains 12g potassium hydroxide and 0.1g potassiumiodide, drips 11.3mL 6-Mecoral again, back flow reaction 24h.After the cooling, reaction solution is poured in the beaker of 200mL, 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-(ω-hydroxyl hexyloxy) phenylformic acid.Fusing point: 139 ℃; Productive rate: 47%;
(2) take by weighing 6.0g 4-(ω-hydroxyl hexyloxy) phenylformic acid, a small amount of MEHQ in the there-necked flask of 100mL, add 60mL vinylformic acid, stir, dissolve, slowly drip the vitriol oil of 0.5mL98%, heating reflux reaction 24h.After the cooling, reaction solution is poured in the beaker of 200mL, washing, precipitation is filtered, and behind the reusable heat water repetitive scrubbing several times, ethyl alcohol recrystallization gets 4-acryloxy (ω-hexyloxy) phenylformic acid.Fusing point: 90 ℃; Productive rate: 65%;
(3) in being housed, the 100mL there-necked flask of electronic stirring, reflux condensing tube adds the xenol of 16.7g, 40mL tetrahydrofuran (THF) and 2mL pyridine, and drip 2 DMF, the stirring at normal temperature dissolving, slowly drip 0.03mol amylbenzene formyl chloride, normal-temperature reaction 2h, heated and stirred back flow reaction 8h.After screwing out an amount of solvent, residual solution is poured in the big water gaging, filter white solid, remove in a large number to xenol with 1.5% NaOH aqueous solution 150mL washing, adjust pH is to neutral, again with ethanolic soln wash 3 ~ 5 times with flush away remnants to xenol, with acetone recrystallization obtain 4-amylbenzene formic acid-4 '-xenol.Fusing point: 172 ℃; Productive rate: 35%;
(4) in the 250mL there-necked flask, take by weighing 8.8g 4-acryloxy (ω-hexyloxy) phenylformic acid, 6.2g N, N '-dicyclohexylcarbodiimide (DCC) and 0.4g 4-Dimethylamino pyridine (DMAP) are dissolved in the methylene dichloride of 100mL stirring and dissolving.Stir slowly drip down the 4-amylbenzene formic acid-4 that is dissolved with 9.2g '-the dichloromethane solution 100mL of xenol, normal-temperature reaction 2h, back flow reaction 36h.After the cooling, add the 45mL deionized water, behind the stirring 0.5h, filter and get filtrate.Mix with filtrate with dilute hydrochloric acid, 5% sodium carbonate solution respectively, standing demix takes off a layer solution.After steaming most solvents, separate out with methanol extraction, filter, ethyl alcohol recrystallization, get 4-amylbenzene formic acid-4 '-acryloxy (ω-hexyloxy) phenylformic acid is to the xenol dibasic acid esters.Fusing point: 109 ℃; Productive rate: 61%;
Get then 3g liquid crystal monomer 4-amylbenzene formic acid-4 '-acryloxy (ω-hexyloxy) phenylformic acid is to the xenol dibasic acid esters; be dissolved in wiring solution-forming in the 25mL tetrahydrofuran (THF); the 50mL flask that injection vacuumizes; under nitrogen protection, be warming up to 60 ℃; the Diisopropyl azodicarboxylate catalyzer that adds 0.03g; reaction 24h monitors reaction process with infrared spectrometer, observes two keys in the monomer at 1642cm
-1About the stretching vibration peak completely dissolve, illustrate that this polyreaction thoroughly finishes, reactant is poured in the methyl alcohol precipitated then, filter, reusable heat washing with alcohol 3 times, vacuum-drying namely obtain poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the finished product liquid crystal, and its structural formula is as follows:
，
[0014]The clearing point of poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the liquid crystal that adopts in the present embodiment is 315 ℃, and the temperature of the crystal habit completely dissolve of PP is 171 ℃, therefore select 175 ℃ temperature to inquire into the dispersion effect of this nucleator in PP, polarized light microscope observing shows, it is 0.2% blend sample for the content of this nucleator, because the relative content of nucleator is few, and in the time of 175 ℃, can't see fairly obvious liquid crystal property or texture, see Fig. 1 (a), when the content of this nucleator is 2%, can observe its liquid crystal property, see Fig. 1 (b), because under 175 ℃ 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 crystal of adding blend sample 3 preparations in polypropylene gathers (methyl) esters of acrylic acid beta-crystal polypropylene nucleator, 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 β;
Embodiment 3:
At first synthetic double bond containing liquid crystal monomer 4-oxygen in heptan base biphenyl-4 '-methacryloxy (oxyethyl group) benzoic ether, comprise 5 steps:
(1) in the 500mL there-necked flask, adds the xenol of 18.6g, 250mL ethanol, 0.1mol heptyl bromide, heated and stirred begins the aqueous solution 15mL of Dropwise 5 .6g KOH to dissolving fully during backflow, reaction 8h, thick product acetone recrystallization gets 4-oxygen in heptan base biphenyl.Fusing point: 156 ℃; Productive rate: 42%;
(2) take by weighing the 13.8g P-hydroxybenzoic acid in the there-necked flask of 100mL, add 25mL ethanol, stir, dissolving slowly drips the 25mL aqueous solution that contains 12g potassium hydroxide and 0.1g potassiumiodide, drips the 6.6mL ethylene chlorhydrin again, back flow reaction 15h.After the cooling, reaction solution is poured in the beaker of 200mL, 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-hydroxy ethoxy phenylformic acid.Fusing point: 179 ℃; Productive rate: 61%;
(3) take by weighing 5.6g 4-hydroxy ethoxy phenylformic acid, a small amount of MEHQ in the there-necked flask of 100mL, add the 60mL methacrylic acid, stir, dissolve, slowly drip the vitriol oil of 0.3mL 98%, heating reflux reaction 24h.After the cooling, reaction solution is poured in the beaker of 200mL, washing, precipitation is filtered, and behind the reusable heat water repetitive scrubbing several times, ethyl alcohol recrystallization gets 4-methacryloxy ethoxybenzoic acid.Fusing point: 140 ℃; Productive rate: 63%;
(4) in the 250mL there-necked flask, take by weighing 6.3g 4-methacryloxy ethoxybenzoic acid, 5.5g N, N '-dicyclohexylcarbodiimide (DCC) and 0.5g 4-Dimethylamino pyridine (DMAP) are dissolved in the methylene dichloride of 50mL stirring and dissolving.Stir the dichloromethane solution 30mL that slowly drips 4-oxygen in the heptan base biphenyl that is dissolved with 6.4g down, normal-temperature reaction 2h, back flow reaction 24h.After the cooling, add the 25mL deionized water, behind the stirring 0.5h, filter and get filtrate.Mix with filtrate with dilute hydrochloric acid, 5% sodium carbonate solution respectively, standing demix takes off a layer solution.After steaming most solvents, separate out with methanol extraction, filter, ethyl alcohol recrystallization gets white powder.Be liquid crystal monomer 4-oxygen in heptan base biphenyl-4 '-methacryloxy (oxyethyl group) benzoic ether.Fusing point: 121 ℃; Productive rate: 62%;
Get then 2g liquid crystal monomer 4-oxygen in heptan base biphenyl-4 '-methacryloxy (oxyethyl group) benzoic ether; be dissolved in wiring solution-forming in the 20mL toluene; the 50mL flask that injection vacuumizes; under nitrogen protection, be warming up to 60 ℃; the benzoylperoxide catalyst that adds 0.02g; reaction 24h monitors reaction process with infrared spectrometer, observes two keys in the monomer at 1642cm
-1About the stretching vibration peak completely dissolve, illustrate that this polyreaction thoroughly finishes, reactant is poured in the methyl alcohol precipitated then, filter, reusable heat washing with alcohol 3 times, vacuum-drying namely obtain poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of the finished product liquid crystal, and its structural formula is as follows:
Poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of liquid crystal and PP blend:
With poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of above-mentioned liquid crystal and after polypropylene fully mixes by different mass ratioes, 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 poly-(methyl) esters of acrylic acid β of polypropylene/liquid crystal | The brilliant nucleator (mass ratio) of poly-(methyl) esters of acrylic acid β of polypropylene/liquid crystal | The β crystalline phase is to content (%) |
| The contrast sample | 100:0 | 0 |
| Blend sample 1 | 100:0.2 | 68 |
| Blend sample 2 | 100:0.4 | 81 |
| Blend sample 3 | 100:0.6 | 72 |
| Blend sample 4 | 100:1.0 | 67 |
As seen beta-crystal polypropylene nucleating effect of the present invention is fine, account for polypropylene mass ratio 1.0% when following in the nucleator quality that adds, the beta-crystal polypropylene ratio that obtains is more than 68%, and wherein during nucleator massfraction 0.4%, the β crystalline phase that obtains is 81% to content.
Claims (2)
1. a liquid crystal gathers (methyl) esters of acrylic acid beta-crystal polypropylene nucleator, it is characterized in that it is to gather (methyl) acrylate chains as macromolecular skeleton, with liquid crystal unit as side chain, liquid crystal unit comprises flexible spacer, liquid crystal nuclear and alkyl or alkoxyl group, and the general structure of this nucleator is (a):
The preparation method of poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of this liquid crystal may further comprise the steps: at first synthetic double bond containing liquid crystal monomer 4-ethoxybenzoic acid-4 '-acryloxy (oxyethyl group) phenylformic acid Resorcinol dibasic acid esters or 4-amylbenzene formic acid-4 '-acryloxy (ω-hexyloxy) phenylformic acid to xenol dibasic acid esters or 4-oxygen in heptan base biphenyl-4 '-methacryloxy (oxyethyl group) benzoic ether; Then with 2 ~ 5g liquid crystal monomer with 50 ~ 100ml dissolution with solvents, be under 60 ℃ of conditions in temperature, the Diisopropyl azodicarboxylate or the benzoylperoxide catalyst that add 0.02 ~ 0.05g, behind reaction 12 ~ 24h, reactant is poured into precipitation in the methyl alcohol, filtered, use after the washing with alcohol 3 times dryly again, obtain the finished product.
2. poly-(methyl) esters of acrylic acid beta-crystal polypropylene nucleator of a kind of liquid crystal according to claim 1 is characterized in that described solvent is toluene or chloroform or tetrahydrofuran (THF).
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| 孙静等.硅氧烷液晶共聚物作为β 晶成核剂对等规聚丙烯结晶结构与形态的影响.《化学学报》.2010,第68卷(第10期),第1003-1009页. * |
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