CN101987891A - Polyolefin resin and nucleating agent-containing composition - Google Patents
Polyolefin resin and nucleating agent-containing composition Download PDFInfo
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- CN101987891A CN101987891A CN2009101640165A CN200910164016A CN101987891A CN 101987891 A CN101987891 A CN 101987891A CN 2009101640165 A CN2009101640165 A CN 2009101640165A CN 200910164016 A CN200910164016 A CN 200910164016A CN 101987891 A CN101987891 A CN 101987891A
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- benzylidene
- sorbyl alcohol
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- alcohol
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Abstract
The invention discloses a polyolefin resin and nucleating agent-containing composition. The composition is characterized in that: a nucleating agent is a polyalcohol diacetal-silica gel graft with a general formula (I). The polyolefin resin and nucleating agent-containing composition of the invention improves the stability of organic acetals, is highly environmentally-friendly, reduces the production cost, and particularly has remarkably improved mechanical properties and thermal properties.
Description
Technical field
The present invention relates to a kind of composition that contains novel nucleator and polyolefin resin, be specifically related to a kind of composition that contains polyvalent alcohol two acetals-silica gel grafts nucleator and polyolefin resin.
Background technology
In order to make polyolefin resin have higher transparency, improve its physicals and/or processing characteristics, abroad from the sixties in 20th century polypropylene (PP) transparent nucleater that begins one's study be used for acrylic resin, begin industrial application to the beginning of the eighties in the U.S..Adding nucleator in PP is one of main method of production transparent PP, and nucleator mainly contains α and β two classes, polyvalent alcohol acetals nucleator is class α type PP nucleator (Zhao Guiliang, Shi Qinzhi, a Shi Jiangong etc. most widely used and with fastest developing speed, sorbitol acetal class polypropylene nucleater study on the synthesis progress, " China and foreign countries' energy " 2008,13 (1): 90-98).
Polyvalent alcohol acetals nucleator be with polyvalent alcohol (being generally sorbyl alcohol or Xylitol) and phenyl aldehyde or its substitutive derivative under the effect of acid catalyst, the product of aldol reaction gained takes place, with sorbyl alcohol and phenyl aldehyde or its substitutive derivative be raw material synthetic acetals nucleator general structure as shown in Equation 1:
Wherein, R
1=R
2=H, alkyl (C
1-C
6), alkoxyl group, hydroxyl or halogen atom.Need to prove that with sorbyl alcohol and phenyl aldehyde and the synthetic acetal of derivative thereof, target product is the as above acetal of structure,
Be that aldehyde and sorbyl alcohol form 1,3:2,4 two acetals.
It is raw material with sorbyl alcohol and phenyl aldehyde that USP3721682 discloses a kind of, under dehydration catalyst (sulfuric acid or phosphoric acid) effect, under 68 ℃-73 ℃, react in the azeotropic system with hexanaphthene and dewatering agent formation and synthesize 1,3:2, the method for 4-two (benzylidene) sorbyl alcohol (being called for short DBS).DBS can be used for the transparent modified of PP, but discharges the aldehyde flavor owing to easily taking place to decompose in the processing use, seldom uses now.USP4314039 discloses 1,3:2, the synthetic method of 4-two (to the methyl benzylidene) sorbyl alcohol (being called for short MDBS).USP5135975, USP5731474 disclose 1,3:2, the synthetic method of 4-two (3, the 4-dimethyl benzylidene) sorbyl alcohol (being called for short DMDBS).USP4371654 discloses with halogeno-benzene formaldehyde or has mixed the method that aromatic aldehyde is the synthetic corresponding acetal nucleator of raw material; USP6245843, USP4388119 disclose the dressing that employing organic carboxyl acid (as mountain Yu acid, stearic acid or Palmiticacid) is DBS, to alleviate the method for DBS smell; It is the method for the synthetic DBS of catalyzer with hydrochloric acid that USP4562265 discloses; USP4902807, USP4429140, USP5973043 disclose the aromatic aldehyde of different substituents (sec.-propyl, chlorine atom, to ethyl, methoxyl group, to nitro) and the method for sorbyl alcohol or the synthetic acetals nucleator of Xylitol; USP4954291, USP5015684 disclose with the method for mixed aldehyde (as 2,4-dimethylbenzaldehyde and phenyl aldehyde) with the synthetic compound sorbitol acetal nucleator of sorbyl alcohol; USP5198484 discloses ultrafine particulate sorbitol acetal nucleator DBS and the application of MDBS in PP; USP6102999 is disclosed to be liquid compound system and the application thereof that sorbitol acetal class nucleator and tensio-active agent constitute.
The Chinese patent 96192324.5 of New Japan Chem Co., Ltd, CN1324887A disclose a kind of sorbyl alcohol two acetal hexagonal crystals and have contained their resin nucleating agent, be to change two acetals into hexagonal (but the XRD figure that does not provide the different crystal structure is composed) by common cubic system by certain method, claim two acetal nucleators of structure of hexagonal crystal can prevent from flake and variable color on layered product, to occur, but the molecular structure of two acetal nucleators does not change.
The Chinese patent ZL98802251.6 of New Japan Chem Co., Ltd discloses the method for particulate diacetal composition, its preparation method and polyolefine resin composition and moulded parts, said polyolefin nucleating agent is to be that two acetal powder of formula 1 mix with tackiness agent with structure, its advantage is the fusing point that has reduced nucleator, help the dispersion of nucleator in polyolefine, its shortcoming is a complicated process of preparation, improve the cost of nucleator, also correspondingly improved the polyolefine resin composition that contains this nucleator and the cost of moulded parts thereof.The molecular structure of two acetals does not have essential change simultaneously.
The Chinese patent ZL98801468.8 of New Japan Chem Co., Ltd discloses two acetal compositions, has prepared the patent of the method for said composition, the polyolefin nucleating agent that contains said composition, polyolefine resin composition and moulded parts, and this invention provides a kind of particle or pulverous two acetal compositions; The method for preparing said composition; The polyolefin resin nucleating agent that contains said composition; The moulded parts that contains nucleator and polyolefine resin composition and polyolefin resin; Described two acetal compositions of this patent contain a kind of two acetals at least as 1,3:2,4-dibenzylidene-D-sorbyl alcohol or the substituted derivative of its parent nucleus and at least a tackiness agent (being selected from part salt, sulfuric acid, sulfonate, phosphate ester salt, phosphoric acid ester, phosphorous acid ester and neutrality or the slightly acidic monobasic organic acid aluminium salt of neutrality or slightly acidic monobasic organic acid, neutrality or slightly acidic poly-basic organic acid, neutrality or slightly acidic poly-basic organic acid).The advantage of this invention is the fusing point that has reduced by two acetals to a certain extent, makes two acetals at low temperature or be dissolved in the polyolefine in the short period of time.But the complicated process of preparation of two acetal compositions has improved the cost of nucleator and subsequent product thereof.Simultaneously because two acetals of this invention still are conventional sorbyl alcohol two acetals, so the mechanical property of polyolefin resin such as rigidity are not obviously improved.
The Chinese patent ZL98801860.8 of New Japan Chem Co., Ltd discloses the method for recrystallizing diacetal in polyolefin resin, relate to a kind of in non-yellowing polyolefin resin the recrystallization structure formula as shown in Equation 1 two acetals or its ring substitutive derivative method, a kind of polyolefin resin plastic that contains the recrystallizing diacetal that can pass through described recrystallization method acquisition, a kind of preparation contains the method by the polyolefin resin pill of two acetals that adopt described recrystallization method recrystallization, polyolefin resin pill with available aforesaid method acquisition, also cool off the method that this melts is produced the polyolefin resin mo(u)lded item with a kind of rapidly by under a temperature that is not less than the sol-gel transition temperature in heating period, heating and melt described pill, and can be by the polyolefin resin mo(u)lded item of said method acquisition.Two acetal compositions of this invention contain the basic cpd in the group that at least a free alkali metal, alkali metal hydroxide, alkaline earth salt and the alkaline earth metal hydroxides of 10-5000ppm form, and/or a kind of organic amine of 1000-80000ppm.This two acetal composition complicated process of preparation, use cost is higher.
The Chinese patent ZL02807297.9 of New Japan Chem Co., Ltd discloses two acetal compositions, the polyolefin nucleating agent that contains this two acetal composition, the polyolefine resin composition that contains this two acetal composition, produce the method and the moulded product of this resin combination, two acetal compositions of this invention comprise (A) two acetals as 1,3:2,4-two (benzylidene)-D-sorbyl alcohol, (B) sulfuric acid and (C) aliphatics monocarboxylic acid, composition (B) and composition (C) are dispersed among the particle of granular or Powdered two acetal compositions, with two acetal compositions is benchmark, the ratio that composition (B) exists is 0.3-5wt%, and composition (B) and total amount (C) are not more than 7wt%; The invention also discloses the polyolefine resin composition that contains this two acetal composition and polyolefin resin; Be used to prepare the method for resin combination; And prepare moulded work by the molding polyolefine resin composition.Though this two acetal composition can play the effect that reduces fusing point and improve the nucleator dispersiveness, but this two acetal compositions complicated process of preparation, cost obviously raises, and causes the cost of the polyolefin compositions that contains two acetal compositions and moulded parts thereof to rise simultaneously.
Yet the polyolefin resin that contains above-mentioned two acetals nucleators, still has the big shortcoming of smell, the polyolefin resin that contains two acetal compositions of various modifications processing, though have certain progress (Wang Xiaoqiang on the two acetal smells overcoming, Li Jichun, Sorbitol dibenzal class nucleator removes the method for smell, " petrochemical technology and application ", 2000,20 (4): 268-272), but not improvement in essence, and, increased burden to downstream user because the increase of two acetal nucleator costs has caused the increase of polyolefine resin composition cost.
Summary of the invention
At above technological deficiency, the invention provides a kind of polyolefine resin composition that contains novel nucleator and polyolefin resin.
Contain polyolefin resin and nucleator in the polyolefine resin composition of the present invention, described nucleator is for having the polyvalent alcohol two acetals-silica gel grafts of general formula (I):
Wherein, R
1, R
2, R
3, R
4Be H, OH, C independently of one another
1-C
6Alkyl, C
1-C
6Alkoxy or halogen; N is 0 or 1.
N represents the number of CH-O-group among the present invention; Siliciumatom directly is attached in the general formula (I) 5 or/and 6 Sauerstoffatom combination, and in general formula of the present invention (I), when 5 or 6 s' Sauerstoffatom during not directly in conjunction with Siliciumatom, then this Sauerstoffatom bonded is a hydrogen atom.
Those skilled in the art are not difficult to know in conjunction with this area general knowledge, SiO
2Can the colloidal form there be the SiO in the general formula of the present invention (I)
2Actual is the form of colloidal silica, and therefore, described polyvalent alcohol two acetals-silica gel chemical graft nucleator is a kind of polyvalent alcohol two acetals and silica gel bonded grafts.
C among the present invention
1-C
6Alkyl includes but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl or cyclopropyl; C
1-C
6Alkoxyl group includes but not limited to methoxyl group, oxyethyl group, propoxy-, isopropoxy or ring propoxy-etc.; Described halogen includes but not limited to fluorine, chlorine or bromine; Described polyvalent alcohol two acetals include but not limited to two acetals of sorbyl alcohol, Xylitol or glucose.
Among the present invention as embodiment preferred, described polyvalent alcohol two acetals include but not limited to: 1,3:2,4-two (3, the 4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the methyl benzylidene) sorbyl alcohol, 1,3:2,4-(3, the 4-dimethyl benzylidene/to the methyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the ethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to ethyl benzylidene/3, the 4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to methyl benzylidene /) sorbyl alcohol to the ethyl benzylidene, 1,3:2,4-two (benzylidene) sorbyl alcohol, 1,3:2,4-two (to the chlorine benzylidene) sorbyl alcohol, 1,3:2,4-(to chlorine benzylidene /) sorbyl alcohol to the methyl benzylidene, 1,3:2,4-(to chlorine benzylidene/3,4 dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/benzylidene) sorbyl alcohol, 1,3:2, the arbitrary composition of 4-(to a chlorine benzylidene/bromine benzylidene) sorbyl alcohol or above-mentioned polyvalent alcohol two acetals.
Polyolefin resin of the present invention can be the polyolefin resin of this area routine, and the present invention selects the polyolefin resin have 5-100%, preferably to have 15-95% degree of crystallinity.
Polyolefin resin of the present invention includes but not limited to polyvinyl resin, acrylic resin, polybutylene-based resin, ethylene-propylene-butadiene copolymer resin or similar ter-polymer resin, methylpent thiazolinyl resin or polybutadiene, or their any mixture.
As embodiment preferred, described polyvinyl resin is high density polyethylene(HDPE), middle density degree polyethylene, new LDPE (film grade) or has at least 50% (W%), preferably isotactic or the syndiotactic ethylene random or the segmented copolymer of at least 70% (W%) ethylene content.
Described acrylic resin is alfon or has at least 50% (W%), preferably isotactic of at least 70% (W%) propylene content or the random or segmented copolymer of syndiotactic propylene.
Described polybutene resin is chevron or has at least 50% (W%), preferably isotactic or the syndiotactic butene random or the segmented copolymer of at least 70% (W%) butene content.
Described methylpent thiazolinyl resin is the methylpentene homopolymer or has at least 50% (W%), preferably the isotactic or the random or segmented copolymer of syndiotactic methylpentene of at least 70% (W%) methylpentene content.
The comonomer that can form various above-mentioned multipolymers includes but not limited to ethene, propylene, butylene, amylene, hexene, heptene, octene, decene, undecylene, dodecylene, (methyl) vinylformic acid and ester, vinyl-acetic ester or toxilic acid, or their any mixture.
The present invention contains in the composition of polyolefin resin and nucleator, polyolefin resin can combine this area routine by those skilled in the art with the ratio of nucleator and determine, as long as can obtain the nucleogenesis of required two acetal grafting silica gel nucleators, the quantity of adding polyolefin resin nucleating agent of the present invention is not particularly limited, as embodiment preferred, in mass, described polyolefin resin is 100 with the ratio of nucleator: 0.01-5; Further the preferred alkenes resin is 100 with the ratio of nucleator: 0.03-3.
In the composition of the present invention, polyvalent alcohol two acetals of described general formula (I)-silica gel grafts can adopt the method for this area routine to be prepared, and as embodiment preferred, the present invention adopts following method preparation:
In reactor, under agitation condition, with polyvalent alcohol add make it in the organic solvent dissolving, add aromatic aldehyde then, add catalyzer and silicon-containing compound afterwards again, room temperature-80 ℃ following reaction 2-10 hour, add basic solution at last, pH 〉=10 that make reaction soln are with termination reaction, after filtration, washing, drying treatment, promptly obtain two acetals-silica gel grafting nucleator.
As embodiment preferred, the mol ratio of aromatic aldehyde described in the inventive method and polyvalent alcohol is 1: 1.85-2.15.
Among the preparation method of polyvalent alcohol two acetals of the present invention-silica gel nucleator, described aromatic aldehyde is for being the aromatic aldehyde of parent nucleus with the phenyl aldehyde, and its substituting group includes but not limited to C
1-C
6Alkyl, C
1-C
6Alkoxyl group, hydroxyl or halogen; C
1-C
6Alkyl includes but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl or cyclopropyl; C
1-C
6Alkoxyl group includes but not limited to methoxyl group, oxyethyl group, propoxy-, isopropoxy, ring propoxy-etc.; Described halogen includes but not limited to fluorine, chlorine or bromine; As embodiment preferred, described aromatic aldehyde is p-tolyl aldehyde, to ethylbenzene formaldehyde, 3,4-dimethylbenzaldehyde, 4-chloro-benzaldehyde, 3-bromobenzaldehyde or p-Fluorobenzenecarboxaldehyde, or they make up arbitrarily.
As embodiment preferred, two acetals of polyvalent alcohol described in the preparation method of the present invention include but not limited to two acetals of sorbyl alcohol, Xylitol or glucose.
Organic solvent described in polyvalent alcohol two acetals of the present invention-silica gel nucleator preparation method can be selected from lower molecular weight alcohols-as methyl alcohol, ethanol or Virahol; Also can be selected from lower molecular weight ethers-as ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether etc.; Can also be lower molecular weight hydrochloric ether-as methylene dichloride, chloroform etc.; Can also be the arbitrary combination of above-mentioned organic solvent, add-on be so that polyvalent alcohol fully is dissolved as suitable.
Catalyzer described in the inventive method is an an acidic catalyst, can be selected from mineral acid, as include but not limited to sulfuric acid, hydrochloric acid, phosphoric acid etc., can also be selected from organic acid, as include but not limited to Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA), thionamic acid, trifluoroacetic acid etc., can also be any two or more combination in the above-mentioned acid.
Silicon-containing compound described in the preparation method of the present invention is alkyl silicate or silica gel; Wherein alkyl silicate includes but not limited to quanmethyl silicate or tetraethyl orthosilicate.
As further preferred embodiment, the temperature of reaction among the preparation method of the present invention is a room temperature-60 ℃; Reaction times is 4-7 hour.
Among the preparation method of the present invention, described basic cpd is for being the compound or the mixture of alkalescence in water, preferred sodium, potassium, rubidium, caesium, calcium or the oxyhydroxide of barium or their soluble carbon hydrochlorate or supercarbonate, concrete example is as including but not limited to sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, hydrated barta, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus.
Preparation method's of the present invention reaction process can directly be carried out in air atmosphere, and does not need the protection of rare gas element; In reaction, do not need simultaneously to remove the water that reaction generates by the form that forms low-carbon alcohol-low-carbon alkanes azeotrope, but water that reaction generates is absorbed by the mode of alkyl silicate in the adding system such as tetraethyl orthosilicate " on-the-spot hydrolysis ", on the one hand " absorption " water that generates of reaction, reaction is carried out to the right; On the other hand, the silica gel that generates of alkyl silicate hydrolysis at the scene with two acetals on unreacted hydroxyl generation condensation and generate target product of the present invention-two acetals-silica gel grafting nucleator.
One-step synthesis is adopted in the preparation of polyvalent alcohol two acetals of the present invention-silica gel grafting nucleator, its principle is: when the synthetic two acetal polyolefin nucleating agents of polyvalent alcohol and aromatic aldehyde, be target product generally with two acetals, when forming two acetals, also have 1-2 unreacted hydroxyl in the acetal molecule, and produce two molecular waters, the hydroxyl in the activated silica gel can with the hydroxyl generation condensation reaction in the acetal molecule, and make silica gel and hydroxyl grafting; For example, with the sorbyl alcohol is example, in the sorbitol acetal synthetic system, add alkyl silicate such as tetraethyl orthosilicate simultaneously, the water generation hydrolysis reaction that generates when then tetraethyl silicate is will be with acetal synthetic and generate silanol, the activity hydroxy of silanol also can be with hydroxyl generation condensation in the two acetal molecules and is made silica gel and two acetals be able to grafting, generates two acetals-silica gel grafting nucleator.In the presence of acid catalyst, synthesize 1 with sorbyl alcohol, phenyl aldehyde and tetraethyl orthosilicate, 3:2,4-two (benzylidene) sorbyl alcohol-silica gel grafting nucleator is an example, at first in the presence of an acidic catalyst, sorbyl alcohol and phenyl aldehyde generation condensation reaction are according to the mol ratio of raw material, reaction is controlled at 1,3:2 in the stage of 4-two (benzylidene) sorbyl alcohol, sees following reaction formula (1); Water generation hydrolysis reaction in tetraethyl orthosilicate and the reaction system, generate tetrasilicic acid, tetrasilicic acid has very high reactive behavior, may generate poly-silicic acid or silica gel (seeing reaction formula (2)) by autohemagglutination on the one hand, the unreacted hydroxyl of activity hydroxy and sorbyl alcohol (being 5 or 6) is because of the shrink bonding on the other hand, become 1,3:2,4-two (benzylidene) sorbyl alcohol-silica gel " grafts ".The formula II of face or formula III as follows
Si(OC
2H
5)
4+2H
2O＝Si(OH)
4+4C
2H
5OH
(2)
(SiO in formula II and the formula III
2) expression silica gel group Siliciumatom directly and sorbyl alcohol hydroxyl bonding; Perhaps silica gel group (SiO
2) Siliciumatom directly and 5 and 6 hydroxyl bondings of sorbyl alcohol.
The present inventor has also measured the FT-IR spectrogram of the polyvalent alcohol two acetals-silica gel grafting nucleator of various embodiments of the present invention preparation, although the composition difference of each embodiment sample, the basically identical as a result of FT-IR is at 1090cm
-1Near have the strong absorption of Si-O-Si.This be because IR be molecular spectrum, reflection be the vibration and the case of bending of the chemical bond in the product molecule.In the spectrogram at 1169cm
-1, 1125cm
-1And 1098cm
-1About three places the charateristic avsorption band of acetal, 835cm all appear
-1About locate to be contraposition disubstituted benzene ring absorption peak.At 1090cm
-1Near be the strong absorption of Si-O-Si, show that the effective chemical grafting has taken place for silica gel and two acetals.
The preparation method of composition that the present invention contains polyolefin resin and nucleator is the preparation method of this area routine, only needs to adopt the method for this area routine can obtain composition of the present invention in the nucleator introducing polyolefin resin of the present invention.As long as can obtain composition required for the present invention, can be prepared by any ordinary method, and have no particular limits.
For example, in the homopolymerization isotactic isotactic polyprophlene resin of 100 mass parts, add the two acetals-silica gel grafting nucleator of 0.22 mass parts, in stirrer,,, under 220 ℃, carry out granulation, compressing tablet then with the mixture melt kneading with both uniform mixing.
Compared with prior art, it is high that polyolefine resin composition of the present invention has the transparency, and the advantage of mechanical property and good in thermal property has also reduced cost simultaneously, and its concrete characteristics are as follows:
(1) nucleator in the polyolefine resin composition of the present invention carries out grafting with organic acetal and activated silica gel, and inorganic silica gel and organic acetal are organically combined, and has improved the stability of organic acetal in the composition;
(2) the chemical graft acetal nucleator smell in the polyolefine resin composition of the present invention obviously reduces, and the environmental-protecting performance of polyolefin resin of the present invention is obviously improved, and helps the healthy of plastic working personnel;
(3) polyolefine resin composition of the present invention does not increase use cost;
(4) chemical graft nucleator of the present invention is under the usage quantity situation identical with similar non-grafting acetal nucleator, and use properties is better than or is equivalent to non-grafting acetal nucleator;
(5) chemical graft nucleator of the present invention is used for the transparent modified of plastics with cheap inorganic silica gel and organic acetal grafting, and addition does not increase, so the cost of nucleator obviously reduces;
(6) synthesis technique of chemical graft nucleator of the present invention is simple, in building-up process, does not produce three waste discharge, belongs to process for cleanly preparing;
(7) mechanical property height and the thermal characteristics that contains the polyolefine resin composition of silica gel graft modification two acetal nucleators obviously improves, and do not have the appearance such as flake that produce because nucleator disperses not good.
Description of drawings
Fig. 1 is the infrared spectrogram of embodiment 1 gained nucleator;
Fig. 2 is the infrared spectrogram of embodiment 2 gained nucleators;
Fig. 3 is the infrared spectrogram of embodiment 3 gained nucleators;
Fig. 4 is the infrared spectrogram of embodiment 4 gained nucleators;
Fig. 5 is the infrared spectrogram of embodiment 5 gained nucleators.
Embodiment
For further specifying implementation process of the present invention, the spy provides below with reference to embodiment and comparing embodiment, but the present invention is not limited to reference example and comparing embodiment.
Adopt following method to measure and estimate the mist degree and the mechanical property of polyolefin compositions of the present invention:
Use haze meter according to the mist degree of GB/T 2410-1980 canonical measure thickness as the polyolefine resin composition of 1.0mm.Measured value is more little, and transparency is good more.
Tc according to ASTM D3418-03 standard test polyolefine resin composition.Measured value is big more, and crystal property is good more.
Stretching yield stress according to GB/T1040.2-2006 standard test polyolefine resin composition.Measured value is big more, and rigidity is good more.
Modulus in flexure according to GB/T 9341-2000 standard test polyolefine resin composition.Measured value is big more, and rigidity is good more.
Load deformation temperature (0.45MPa) according to GB/T 1634.2-2004 standard test polyolefine resin composition.Measured value is high more, and heat-resistant stability is good more.
Notched izod shock strength (23 ℃) according to GB/T 1843-1996 standard test polyolefine resin composition.Measured value is big more, and toughness is good more.
Measure the fracture tension strain of polyolefine resin composition according to GB/T 1040.2-2006 (50mm/min).Measured value is big more, and toughness is good more.
Stress in bending (deciding amount of deflection) according to GB/T 9341-2000 standard test polyolefine resin composition.Measured value is big more, and rigidity is good more.
Melt temperature according to ASTM D3418-03 standard test polyolefine resin composition.Measured value is high more, and the thermotolerance of resin is good more.
Crystallization heat content and melting enthalpy according to ASTM D3418-03 standard test polyolefine resin composition.
The preparation of nucleator
Embodiment 11,3:2, the preparation of 4-two (3, the 4-dimethyl benzylidene) sorbyl alcohol-silica gel grafting nucleator.
In the four-hole reactor of agitator, feed hopper, thermometer and condenser is housed, add sorbyl alcohol 18.2g, 100cm
3Methyl alcohol, stirring and dissolving.Under agitation then, add 28.3g 3,4-dimethylbenzaldehyde and tosic acid 1g, tetraethyl orthosilicate 20.8g is behind reaction 7h under 50 ℃, with aqueous sodium hydroxide solution neutralization reaction system, make its pH 〉=10, add the tap water washing, filter, the dry white powder that gets.
The infrared spectra of sample is at 1090cm
-1Near the strong absorption of Si-O-Si is arranged, show that the hydroxyl on Siliciumatom and the sorbyl alcohol has carried out effective bonding.The infrared spectrogram of sample is seen accompanying drawing 1.The sample of present embodiment preparation is abbreviated as DMDBS-SiO in the following embodiments
2Under the same conditions, the sample that does not add tetraethyl orthosilicate preparation is called DMDBS.
Embodiment 21,3:2, the preparation of 4-two (to the methyl benzylidene) sorbyl alcohol-silica gel grafting nucleator.
In the four-hole reactor of agitator, feed hopper, thermometer and condenser is housed, add sorbyl alcohol 18.2g, ethanol 100cm
3, stirring and dissolving.Under agitation then, add 24.6g p-tolyl aldehyde and Phenylsulfonic acid 1.2g, tetraethyl orthosilicate 20.8g after reacting 7h under 55 ℃, with calcium hydroxide aqueous solution neutralization reaction system, makes its pH 〉=10, adds tap water washing, filtration, the dry white powder that gets.
The FTIR spectrogram of sample is at 1090cm
-1Near the strong absorption of Si-O-Si is arranged, show that the hydroxyl on Siliciumatom and the sorbyl alcohol has carried out effective bonding.The infrared spectrogram of sample is seen accompanying drawing 2.The sample of present embodiment preparation is abbreviated as MDBS-SiO in the following embodiments
2
Embodiment 31,3:2, the preparation of 4-two (3,4-dimethyl benzylidene/to the methyl benzylidene) sorbyl alcohol-silica gel grafting nucleator.
In the four-hole reactor of agitator, feed hopper, thermometer and condenser is housed, add sorbyl alcohol 18.2g, methyl alcohol 100cm
3, stirring and dissolving.Under agitation then, add 3,4-dimethylbenzaldehyde 13.2g and p-tolyl aldehyde 12.3g, p-methyl benzenesulfonic acid 1.5g, quanmethyl silicate 15.2g is behind reaction 7h under 52 ℃, with potassium hydroxide aqueous solution neutralization reaction system, make its pH 〉=10, add the tap water washing, filter, the dry white powder that gets.
The FTIR spectrogram of sample is at 1090cm
-1Near the strong absorption of Si-O-Si is arranged, show that the hydroxyl on Siliciumatom and the sorbyl alcohol has carried out effective bonding.The infrared spectrogram of sample is seen accompanying drawing 3.The sample of present embodiment preparation is abbreviated as DMDBS/MDBS-SiO in the following embodiments
2
Prepared 3 respectively according to embodiment 3 same methods, 4-dimethylbenzaldehyde/p-tolyl aldehyde (mol)=4/1,3/1,5 samples of 1/3,1/4 and 1/5 are respectively sample 1, sample 2, sample 3, sample 4 and sample 5, and they are white powder.
The FTIR spectrogram of sample is at 1090cm
-1Near the strong absorption of Si-O-Si is arranged, show that the hydroxyl on Siliciumatom and the sorbyl alcohol has carried out effective bonding.The infrared spectrogram of sample 1-5 is seen accompanying drawing 4.
Embodiment 5 is 1 of silicon source with silica gel, 3:2, the preparation of 4-two (3, the 4-dimethyl benzylidene) sorbyl alcohol-silica gel grafting nucleator.
In the four-hole reactor of agitator, feed hopper, thermometer and condenser is housed, add sorbyl alcohol 18.2g sorbyl alcohol, 100cm
3Methyl alcohol, stirring and dissolving.Under agitation then, add 28.3g3,4-dimethylbenzaldehyde and tosic acid 1g, silica gel 0.6g after reacting 6h under 50 ℃, with baryta water neutralization reaction system, makes its pH 〉=10, adds tap water washing, filtration, the dry white powder that gets.
The FTIR spectrogram of sample is at 1090cm
-1Near the strong absorption of Si-O-Si is arranged, show that the hydroxyl on Siliciumatom and the sorbyl alcohol has carried out effective bonding.The infrared spectra of sample is seen accompanying drawing 5.The sample of present embodiment preparation is abbreviated as DMDBS-SiO in the following embodiments
2 *
The preparation of polyolefine resin composition
Preparation method: the two acetals-silica gel grafting nucleator that in the homopolymerization isotactic isotactic polyprophlene resin of 100 mass parts, adds 0.22 mass parts, in stirrer with both uniform mixing, with the mixture melt kneading, under 220 ℃, carry out granulation, compressing tablet then.
Embodiment 6-9 is according to the method that is used to prepare polyolefine resin composition that provides above, the mass ratio that provides according to table 1.Millad 3988 is a U.S. Milliken company product.Preparation be that every performance of the resin combination of base-material is listed in table 1 with the homo-polypropylene.
Table 1
The data of table 1 show, compare with Millad 3988, add DMDBS-(SiO
2)
nThe indexs such as Tc, draft temperature, stretching yield stress, modulus in flexure and load deformation temperature of polypropene composition all be significantly improved.
Embodiment 10-13 is according to the method that is used to prepare polyolefine resin composition that provides above, and the addition of nucleator is 2.2wt ‰.NA-21 is the electrochemical company of a Japanese rising sun imported product.Preparation be that every performance of the resin combination of base-material is listed in table 2 with the atactic copolymerized polypropene.
Table 2
The data of table 2 show: compare with NA-21, the mist degree of acrylic resin obviously descends, and other mechanical propertys and thermal characteristics also obviously are better than adding the acrylic resin of NA-21.
Embodiment 14-15 is according to the method that is used to prepare polyolefine resin composition that provides above, and the addition of nucleator is 2.2wt ‰.NA-21 is the electrochemical company of a Japanese rising sun imported product.Preparation be that every performance of the resin combination of base-material is listed in table 3 with the crushing-resistant copolymerization polypropylene.
Table 3
The data of table 3 show: compare the mechanical property of the acrylic resin of interpolation nucleator of the present invention and the acrylic resin that thermal characteristics obviously is better than adding NA-21 with NA-21.
Comparative example 6-9 is according to the method that is used to prepare polyolefine resin composition that provides above, the silica gel that provides according to table 4 accounts for the mass percent of DMDBS, silica gel and DMDBS are carried out uniform physical mixed, as nucleator, its addition is 2.2 ‰, preparation be that every performance of the resin combination of base-material is listed in table 4 with the homo-polypropylene.
Table 4
The data of table 4 show: silica gel and DMDBS physics are compound to the MODIFICATION OF POLYPROPYLENE effect, no matter are the modified effects of the composite nucleating agent that should mechanical property all forms not as good as chemical graft of the mist degree of sample.
Claims (10)
1. a composition that contains polyolefin resin and nucleator is characterized in that, described nucleator is for having the polyvalent alcohol two acetals-silica gel grafts of general formula (I):
Wherein, R
1, R
2, R
3, R
4Be H, OH, C independently of one another
1-C
6Alkyl, C
1-C
6Alkoxy or halogen; N is 0 or 1.
2. composition according to claim 1 is characterized in that, described C
1-C
6Alkyl is methyl or ethyl; Described C
1-C
6Alkoxyl group is a methoxy or ethoxy; Described halogen is fluorine, chlorine or bromine; Described polyvalent alcohol two acetals are two acetals of sorbyl alcohol, Xylitol or glucose.
3. composition according to claim 2, it is characterized in that, described polyvalent alcohol two acetals are: 1,3:2,4-two (3, the 4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the methyl benzylidene) sorbyl alcohol, 1,3:2,4-(3, the 4-dimethyl benzylidene/to the methyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the ethyl benzylidene) sorbyl alcohol, 1,3:2,4-is (to ethyl benzylidene/3, the 4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to methyl benzylidene /) sorbyl alcohol to the ethyl benzylidene, 1,3:2,4-two (benzylidene) sorbyl alcohol, 1,3:2,4-two (to the chlorine benzylidene) sorbyl alcohol, 1,3:2,4-(to chlorine benzylidene /) sorbyl alcohol to the methyl benzylidene, 1,3:2,4-is (to chlorine benzylidene/3,4 dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/benzylidene) sorbyl alcohol, 1,3:2, the arbitrary composition of 4-(to a chlorine benzylidene/bromine benzylidene) sorbyl alcohol or above-mentioned polyvalent alcohol two acetals.
4. composition according to claim 3 is characterized in that, described polyolefin resin is the polyolefin resin with 5-100%, preferred 15-95% degree of crystallinity.
5. composition according to claim 4, it is characterized in that, described polyolefin resin is polyvinyl resin, acrylic resin, polybutylene-based resin, ethylene-propylene-butadiene copolymer resin, methylpent thiazolinyl resin or polybutadiene, or their any mixture.
6. composition according to claim 5, it is characterized in that, described polyvinyl resin is high density polyethylene(HDPE), middle density degree polyethylene, new LDPE (film grade) or has at least 50%, the isotactic of preferred at least 70% ethylene content or the random or segmented copolymer of syndiotactic ethene; Described acrylic resin is alfon or has at least 50%, the isotactic or the random or segmented copolymer of syndiotactic propylene of preferred at least 70% propylene content; Described polybutene resin is chevron or has at least 50%, isotactic or the syndiotactic butene random or the segmented copolymer of preferred at least 70% butene content; Described methylpent thiazolinyl resin is the methylpentene homopolymer or has at least 50%, the isotactic or the random or segmented copolymer of syndiotactic methylpentene of preferred at least 70% methylpentene content.
7. composition according to claim 6, in the described composition, in mass, polyolefin resin is 100 with the ratio of nucleator: 0.01-5; Be preferably 100: 0.03-3.
8. according to the described arbitrary composition of claim 1-7, it is characterized in that, described nucleator adopts the preparation of following method: in reactor under agitation condition, polyvalent alcohol added in the organic solvent dissolve, add aromatic aldehyde then, add catalyzer and silicon-containing compound afterwards again, room temperature-80 ℃ following reaction 2-10 hour, add basic solution at last, pH 〉=10 that make reaction soln promptly obtain two acetals-silica gel grafting nucleator with termination reaction through aftertreatment.
9. composition according to claim 8 is characterized in that, described organic solvent is methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, methylene dichloride or chloroform, or their any mixture; Described catalyzer is sulfuric acid, hydrochloric acid, phosphoric acid Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA) or trifluoroacetic acid; Described silicon-containing compound is alkyl silicate or silica gel, is preferably quanmethyl silicate or tetraethyl orthosilicate; Described basic cpd is the oxyhydroxide of sodium, potassium, rubidium, caesium, calcium or barium or their soluble carbon hydrochlorate or supercarbonate.
10. composition according to claim 8 is characterized in that, the mol ratio of described aromatic aldehyde and polyvalent alcohol is 1: 1.85-1: 2.15; Described temperature of reaction is a room temperature-60 ℃; Reaction times is 4-7 hour.
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| CN103087073A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Preparation method of polyolefin resin nucleating agent |
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| CN104163984A (en) * | 2013-10-31 | 2014-11-26 | 中国石油化工股份有限公司 | Polyolefin resin composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100842164B1 (en) * | 2001-03-27 | 2008-06-27 | 신닛폰 리카 가부시키가이샤 | Diacetal Composition, Nucleating Agent Containing the Composition for Polyolefin, Polyolefin Resin Composition Containing the Diacetal Composition, Process for Producing the Resin Composition, and Molded Object |
| US8022133B2 (en) * | 2005-01-28 | 2011-09-20 | Milliken & Company | Co-additive compositions and methods for applying co-additive compositions into nucleated polymer compounds |
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