CN104211985A - Aluminum hydroxide-containing nucleating agent and preparation method thereof - Google Patents
Aluminum hydroxide-containing nucleating agent and preparation method thereof Download PDFInfo
- Publication number
- CN104211985A CN104211985A CN201410160385.8A CN201410160385A CN104211985A CN 104211985 A CN104211985 A CN 104211985A CN 201410160385 A CN201410160385 A CN 201410160385A CN 104211985 A CN104211985 A CN 104211985A
- Authority
- CN
- China
- Prior art keywords
- sorbyl alcohol
- nucleator
- alcohol
- bis
- benzylidene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC1OC(c2ccccc2)O*(C(CO)O*=C)C1OC(c1ccccc1)O* Chemical compound CC1OC(c2ccccc2)O*(C(CO)O*=C)C1OC(c1ccccc1)O* 0.000 description 2
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nucleating agent and a preparation method thereof. The nucleating agent is a polyol acetal-aluminum hydroxide grafted compound. The nucleating agent substantially improves polyolefin resin transparency, improves organic acetal stability, improves environmental performances and reduces a production cost.
Description
Technical field
The present invention relates to a kind of nucleator and preparation method thereof, nucleator particularly relating to aluminium hydroxide and preparation method thereof.
Background technology
External polypropylene (PP) transparent nucleater that begins one's study from the sixties in 20th century, starts industrial application to the beginning of the eighties in the U.S..At present, the rate of growth of transparent PP goods demand has exceeded the 8%-10% of plain polypropylene goods, has driven the continuous progress of nucleator technology thus.Within 2006, global transparent PP consumption is close to 3,000,000 tons, and the same year, China's transparent PP consumption was more than 250,000 tons, became one of kind that in PP product, speedup is the fastest.In PP, add nucleator is one of main method of production transparent PP, and nucleator mainly contains α and β two class, polyol acetal class nucleator is a class α type PP nucleator (Zhao Guiliang most widely used and with fastest developing speed, Shi Qinzhi, Shi Jiangong etc., Synthetic Research Progress of Sorbitol Acetals Nucleating Agents for Polypropylene, China and foreign countries' energy, 2008,13 (1): 90-98).
Polyol acetal class nucleator is the product that aldol reaction gained occurs under the effect of acid catalyst with polyvalent alcohol (being generally sorbyl alcohol or Xylitol) and phenyl aldehyde or its substitutive derivative, and the general structure of the acetals nucleator being Material synthesis with sorbyl alcohol and phenyl aldehyde or its substitutive derivative is such as formula shown in (A):
Wherein, R
1=R
2=H, alkyl (C
1-C
6), alkoxyl group, hydroxyl or halogen atom.It should be noted that, synthesize acetal with sorbyl alcohol and phenyl aldehyde and derivative thereof, target product is the acetal of as above structure, and namely aldehyde and sorbyl alcohol form 1,3:2, two acetals of 4.
US3721682 disclose a kind of with sorbyl alcohol and phenyl aldehyde for raw material, under dehydration catalyst (sulfuric acid or phosphoric acid) effect, in the azeotropic system formed with hexanaphthene and dewatering agent, Reactive Synthesis 1 at 68 DEG C-73 DEG C, the method of 3:2,4-Sorbitol dibenzal (being called for short DBS).DBS can be used for the transparent modified of PP, but discharges aldehyde taste owing to easily occurring to decompose in processing use procedure, seldom uses now.
US4314039 discloses 1,3:2, the preparation method of 4-bis-(to methylbenzilidene) sorbyl alcohol (being called for short MDBS).US5135975, US5731474 disclose 1,3:2, the synthetic method of 4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol (being called for short DMDBS).The method that it is the corresponding acetal nucleator of Material synthesis that US4371654 discloses with halogenated benzaldehyde or mixing aromatic aldehyde; US6245843, US4388119 disclose the dressing adopting organic carboxyl acid (as behenic acid, stearic acid or Palmiticacid) to be DBS, to alleviate the method for DBS smell; It is the method that catalyzer synthesizes DBS that US4562265 discloses with hydrochloric acid; US4902807, US4429140, US5973043 disclose different substituents (sec.-propyl, chlorine atom, to ethyl, methoxyl group, to nitro) aromatic aldehyde and sorbyl alcohol or Xylitol synthesize the method for acetals nucleator; US4954291, US5015684 disclose the method for synthesizing compound sorbitol acetal nucleator with mixed aldehyde (as 2,4-dimethylbenzaldehyde and phenyl aldehyde) and sorbyl alcohol; US5198484 discloses the application of ultrafine particulate sorbitol acetal nucleator DBS and MDBS in PP; The liquid complex system that forms of sorbitol acetal class nucleator and tensio-active agent and application thereof disclosed in US6102999.CN1840532A discloses one " asymmetric diacetals transparent nucleator and its preparation method and application ", is characterized in adopting mixed aldehyde synthesis to contain two acetal mixts of symmetrical structure and unsymmetric structure simultaneously.In the preparation process of above-mentioned two acetal nucleators, have two basic characteristics, namely reaction process needs the protection of rare gas element, and this adds preparation cost, operation easier undoubtedly; Simultaneously due to the reversibility of acetal building-up reactions, the mode of low-carbon alcohol as methyl alcohol and low-carbon alkanes azeotropic is adopted to remove the water reacting and generate in each patent documentation bar none, move to the direction of generation two acetal to impel reaction, its shortcoming is that azeotrope need be separated, cause reaction process route to extend, cost increases.
In the composition of disclosed polyvalent alcohol (comprising sorbyl alcohol and Xylitol) acetals nucleator, no matter how synthesis technique and catalyzer, dewatering agent change, its common feature is that the target product of synthesis is two acetals with polyvalent alcohol and aromatic aldehyde (mainly phenyl aldehyde and benzene ring substitution group derivative thereof) for raw material.The synthesis of acetal is the reversible reaction that alcohol and aldehyde carry out under the existence of an acidic catalyst, and therefore, acetal is in the process deposited or use, and always discharge aldehyde due to decomposition, this is the main drawback of acetals nucleator.Although people have employed thousand and one way (Wang little Qiang, Li Jichun, Sorbitol dibenzal class nucleator removes the method for smell, " petrochemical technology and application ", 2000,20 (4): 268-272), attempt to overcome the inconvenience that aldehyde taste brings, but still not exclusively satisfactory.
CN101613490B discloses a kind of polyolefin resin nucleating agent, and described nucleator is polyvalent alcohol two acetals-Silicage-polymer-bonded phase thing, and this nucleator improves the stability of organic acetal, improves environmental-protecting performance, but the transparency of polyolefin resin still awaits improving.In addition, the price of silica gel costly.
Summary of the invention
For the above-mentioned defect of prior art, the invention provides following technical scheme, these defects can be overcome.
The invention provides a kind of nucleator, described nucleator is for having the polyvalent alcohol two acetals-aluminium hydroxide 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.
According to nucleator of the present invention, preferably, described C
1-C
6alkyl is methyl or ethyl; Described C
1-C
6alkoxyl group is methoxy or ethoxy; Be fluorine, chlorine or bromine with described halogen.
According to nucleator of the present invention, preferably, described polyvalent alcohol two acetal is two acetals of two acetals of sorbyl alcohol, two acetals of Xylitol or glucose.
According to nucleator of the present invention, preferably, described polyvalent alcohol two acetal is: 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-bis-(to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-(to ethylbenzylidene/3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to methylbenzilidene/to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-bis-(benzylidene) sorbyl alcohol, 1,3:2,4-bis-(p-chlorobenzal base) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/3,4 dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/benzylidene) sorbyl alcohol, the arbitrary composition of 1,3:2,4-(a p-chlorobenzal base/bromine benzylidene) sorbyl alcohol or above-mentioned polyvalent alcohol two acetal.
The present invention also provides a kind of preparation method of above-mentioned nucleator, said method comprising the steps of:
In the reactor under agitation condition, polyvalent alcohol is added in organic solvent and dissolves, then aromatic aldehyde is added, add catalyzer and aluminum contained compound more afterwards, reaction 2 ~ 10 hours at room temperature ~ 80 DEG C, finally add the solution containing basic cpd, make pH >=10 of reaction system with termination reaction, namely obtain described nucleator through aftertreatment.
According to method of the present invention, preferably, the mol ratio of described aromatic aldehyde and polyvalent alcohol is 1:1.85 ~ 1:2.15.
According to method of the present invention, preferably, described organic solvent is selected from one or more of alcohol, ether or hydrochloric ether.
According to method of the present invention, preferably, described organic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, methylene dichloride, chloroform or their any mixture.
According to method of the present invention, preferably, described catalyzer is sulfuric acid, hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA) or trifluoroacetic acid; Be aluminium alcoholates, aluminum alkyls, the halogenide of aluminium or aluminium hydroxide with described aluminum contained compound.
According to method of the present invention, preferably, described basic cpd is the oxyhydroxide of sodium, potassium, rubidium, caesium, calcium or barium, soluble carbonate salt, supercarbonate or soluble phosphate.
Nucleator of the present invention compared with sorbyl alcohol two acetals-Silicage-polymer-bonded phase nucleator, the two is used for polyolefinic transparent modified time, when usage quantity is identical, use the transparency of the polyolefin resin of nucleator of the present invention to be significantly improved.In addition, nucleator of the present invention is raw materials used is aluminum contained compound, and source is wider, and cheaper, gained nucleator cost is lower.
Accompanying drawing explanation
The infrared spectra of the product of Fig. 1 embodiment 1;
Fig. 2 prepares the infrared spectrum of the DMDBS of comparative example 1.
Embodiment
The invention provides a kind of new nucleator, this nucleator can be used as polyolefin resin nucleating agent.Nucleator of the present invention belongs to polyvalent alcohol two acetals-aluminium hydroxide chemical graft nucleator.Nucleator of the present invention is for having the polyvalent alcohol two acetals-aluminium hydroxide 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.
Have in the polyvalent alcohol two acetals-aluminium hydroxide grafts of general formula (I) of the present invention, n represents the number of-CH-O-group; N is 0 or 1.When n is 0, general formula (I) represents pentavalent alcohol two acetals-aluminium hydroxide grafts; When n is 1, general formula (I) represents hexavalent alcohol two acetals-aluminium hydroxide grafts.
In polyvalent alcohol two acetals of the present invention-aluminium hydroxide grafts, aluminium atom is directly combined with the Sauerstoffatom of 5 and/or 6, refers to following formula.When the Sauerstoffatom of 5 or 6 is not directly in conjunction with the aluminium atomic time, then this Sauerstoffatom is combined with hydrogen atom.
As everyone knows, Al (OH)
3can colloid form exist.Have in the polyvalent alcohol two acetals-aluminium hydroxide grafts of general formula (I) of the present invention, Al (OH)
3can exist with the polymeric form of aluminium hydroxide.
Have in the polyvalent alcohol two acetals-aluminium hydroxide grafts of general formula (I) of the present invention, C
1-C
6alkyl includes but not limited to methyl, ethyl, propyl group, sec.-propyl, butyl or cyclopropyl; As preferably, described C
1-C
6alkyl is methyl or ethyl.C
1-C
6alkoxyl group includes but not limited to methoxyl group, oxyethyl group, propoxy-, isopropoxy or ring propoxy-etc.; As preferably, described C
1-C
6alkoxyl group is methoxy or ethoxy.Described halogen includes but not limited to fluorine, chlorine or bromine; As preferably, described halogen is chlorine or bromine.
Have in the polyvalent alcohol two acetals-aluminium hydroxide grafts of general formula (I) of the present invention, described polyvalent alcohol two acetal includes but not limited to two acetals of sorbyl alcohol, Xylitol or glucose.As preferably, described polyvalent alcohol two acetal is two acetals of two acetals of sorbyl alcohol, two acetals of Xylitol or glucose.As more preferably, described polyvalent alcohol two acetal is two acetals of sorbyl alcohol.
As preferred embodiment in the present invention, described polyvalent alcohol two acetal includes but not limited to: 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-bis-(to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-(to ethylbenzylidene/3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to methylbenzilidene/to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-bis-(benzylidene) sorbyl alcohol, 1,3:2,4-bis-(p-chlorobenzal base) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/3,4 dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/benzylidene) sorbyl alcohol, the arbitrary composition of 1,3:2,4-(a p-chlorobenzal base/bromine benzylidene) sorbyl alcohol or above-mentioned polyvalent alcohol two acetal.
As preferred embodiment in the present invention, described polyvalent alcohol two acetal be selected from following material one or more: 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(to methylbenzilidene) sorbyl alcohol, 1,3:2,4-bis-(p-chlorobenzal base) sorbyl alcohol, 1,3:2,4-bis-(a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/to methylbenzilidene) sorbyl alcohol.
Nucleator of the present invention adopts one-step synthesis to be prepared, its principle is: when polyvalent alcohol and aromatic aldehyde synthesize two acetal nucleators, generally with two acetals for target product, while formation two acetal, also have 1-2 unreacted hydroxyl in acetal molecule, and produce two molecular waters; Hydroxyl in the active aluminium hydroxide that aluminum contained compound reaction generates with the hydroxyl generation condensation reaction in two acetal molecules, and can make the hydroxyl grafting in aluminium hydroxide and two acetal molecules.Such as, for sorbyl alcohol, in sorbitol acetal synthetic system, add aluminium alcoholates as aluminum methylate simultaneously, when then aluminum methylate will synthesize with acetal generate water generation hydrolysis reaction and methanol and active aluminium hydroxide, the activity hydroxy of active aluminium hydroxide also can make aluminium hydroxide and two acetals be combined with the hydroxyl generation condensation in two acetal molecules, and generate two acetals-aluminium hydroxide grafting nucleator, methyl alcohol then becomes a part for reaction system solvent.
Synthesize 1,3:2 in presence of an acid catalyst with sorbyl alcohol, phenyl aldehyde and aluminum methylate, 4-bis-(benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator is that example is described in detail.First, under the existence of an acidic catalyst, sorbyl alcohol and phenyl aldehyde generation condensation reaction, according to the mol ratio of raw material, by the stage of reaction controlling at 1,3:2,4-(dibenzylidene) sorbyl alcohol, be shown in following reaction formula (1); And the water generation hydrolysis reaction in aluminum methylate and reaction system, generate aluminium hydroxide and methyl alcohol (see formula (2a)), aluminium hydroxide has very high reactive behavior, its activity hydroxy and the unreacted hydroxyl of sorbyl alcohol (being 5 or 6) can shrink and bonding fast, form 1,3:2,4-bis-(benzylidene) sorbyl alcohol-aluminium hydroxide " grafts ".See formula II below or formula III.Other hydrolysis equations as aluminum contained compounds such as aluminum alkylss are shown in formula (2b), (2c) and (2d) respectively.
Al(OCH
3)
3+3H
2O＝Al(OH)
3+3CH
3OH (2a)
Al(C
2H
5)
3+3H
2O=Al(OH)
3+H
2 (2b)
AlCl
3+3H
2O=Al(OH)
3+3HCl (2c)
AlH
3+3H
2O=Al(OH)
3+3H
2 (2d)
-Al (OH) in formula II and formula III
3represent aluminium hydroxide group, its aluminium atom directly and 5 hydroxyl bondings of sorbyl alcohol; Or its aluminium atom is direct and 6 hydroxyl bondings of sorbyl alcohol.
More specifically, nucleator of the present invention can adopt following methods to be prepared, and said method comprising the steps of:
In the reactor, under agitation condition, polyvalent alcohol is added in organic solvent and make it to dissolve, then add aromatic aldehyde, add catalyzer and aluminum contained compound more afterwards, reaction 2 ~ 10 hours at room temperature ~ 80 DEG C, finally add the solution (basic solution) containing basic cpd, make pH >=10 of reaction system with termination reaction, after filtration, washing, drying treatment, namely obtain nucleator.
In the preparation process in accordance with the present invention, the mol ratio of aromatic aldehyde and polyvalent alcohol can be 1:1.85-2.15; Be preferably 1:1.9-2.1; Be more preferably 1:1.95-2.0.
In the preparation process in accordance with the present invention, described aromatic aldehyde can be take phenyl aldehyde as the aromatic aldehyde of parent nucleus.The substituting group of this aromatic aldehyde 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; Be preferably methyl or ethyl.C
1-C
6alkoxyl group includes but not limited to methoxyl group, oxyethyl group, propoxy-, isopropoxy, ring propoxy-etc.; Be preferably methoxy or ethoxy.Described halogen includes but not limited to fluorine, chlorine or bromine; Be preferably chlorine or bromine.As preferred embodiment, described aromatic aldehyde can be one or more the composition in p-tolyl aldehyde, 3,4-dimethylbenzaldehydes, p-ethylbenzaldehyde, 4-chloro-benzaldehyde, 3-bromobenzaldehyde or p-Fluorobenzenecarboxaldehyde.
As preferred embodiment, the polyvalent alcohol described in preparation method of the present invention includes but not limited to sorbyl alcohol, Xylitol or glucose etc.; Be more preferably sorbyl alcohol.
In the preparation process in accordance with the present invention, described organic solvent is the solvent that can dissolve polyvalent alcohol.Described organic solvent is selected from one or more of alcohol, ether or hydrochloric ether.As preferably, described organic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, methylene dichloride, chloroform or their any mixture.In addition, organic solvent of the present invention can be selected from lower molecular weight alcohols, as methyl alcohol, ethanol or Virahol; Also lower molecular weight ethers can be selected from, as ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether etc.; Lower molecular weight hydrochloric ether can also be selected from, as methylene dichloride, chloroform etc.Described organic solvent can also be the arbitrary combination of above-mentioned organic solvent.The add-on of described organic solvent is suitable to make polyvalent alcohol fully be dissolved as.
In the preparation process in accordance with the present invention, described catalyzer is an acidic catalyst, can be selected from mineral acid, includes but not limited to sulfuric acid, hydrochloric acid, phosphoric acid etc.; Can also organic acid be selected from, include but not limited to Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA), thionamic acid, trifluoroacetic acid etc.; It can also be two or more combination any in above-mentioned acid.Preferably, catalyzer of the present invention is sulfuric acid, hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA) or trifluoroacetic acid.
In the preparation process in accordance with the present invention, described aluminum contained compound is to be hydrolyzed the aluminum contained compound obtaining activity hydroxy, the halogenide of such as aluminium alcoholates, aluminum alkyls, aluminum hydride, aluminium or aluminium hydroxide etc.Wherein, aluminium alcoholates includes but not limited to C
1-C
4the aluminium alcoholates aluminium alcoholates of 1 ~ 4 carbon atom (namely containing); Aluminum alkyls includes but not limited to C
1-C
4the aluminum alkyls of alkyl; The halogenide of aluminium includes but not limited to aluminum fluoride, aluminum chloride or aluminum bromide.
As further preferred embodiment, the temperature of reaction in preparation method of the present invention is room temperature ~ 60 DEG C, is preferably 30 ~ 50 DEG C; Reaction times is 4 ~ 7 hours, is preferably 5 ~ 6 hours.
In the preparation process in accordance with the present invention, described basic cpd is in the compound of alkalescence or mixture in water.As preferably, described basic cpd is the oxyhydroxide of sodium, potassium, rubidium, caesium, calcium or barium, soluble carbonate salt, supercarbonate or soluble phosphate.Object lesson includes but not limited to: sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, hydrated barta, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, sodium phosphate or potassiumphosphate.
In the preparation process in accordance with the present invention, reaction process can directly be carried out in air atmosphere, and does not need the protection of rare gas element; Do not need the form by forming low-carbon alcohol-low-carbon alkanes azeotrope to remove the water of reaction generation in the reaction simultaneously, but the water making reaction generate is absorbed by the mode of the aluminum contained compound added in system as aluminum methylate " on-the-spot hydrolysis ", the water that generates of " absorption " reaction on the one hand, reaction is carried out, and unnecessary water is absorbed to the right by the aluminium hydroxide being hydrolyzed generation; On the other hand, the aluminium hydroxide that generates of aluminum methylate hydrolysis at the scene with unreacted hydroxyl generation condensation on two acetals and generate target product of the present invention-polyvalent alcohol two acetals-aluminium hydroxide grafts nucleator.
Nucleator of the present invention is used for polyolefin resin, significantly can increase the transparency of polyolefin resin.When nucleator of the present invention is used for polyolefin resin, the method for this area routine can be adopted to be incorporated in polyolefin resin by nucleator of the present invention, thus obtain the polyolefine resin composition containing polyvalent alcohol two acetals-aluminium hydroxide grafting nucleator.As long as the nucleogenesis of required polyvalent alcohol two acetal grafting aluminium hydroxide nucleator can be obtained, the interpolation quantity of nucleator of the present invention is not particularly limited.Preferably, the polyolefin resin of every 100 mass parts, needs the amount of nucleator of the present invention to be 0.01 ~ 5 mass parts, is preferably 0.02 ~ 3 mass parts, is more preferably 0.05 ~ 1 mass parts, is more preferably 0.1 ~ 0.5 mass parts.
Nucleator of the present invention can be used as the nucleator of any polyolefin resin in this area.As preferred embodiment, described polyolefin resin can for having the crystalline resins of 5-100%, preferably 15-95% degree of crystallinity.Polyolefin resin of the present invention specifically comprises polyvinyl resin, polypropylene-based resin, polybutylene-based resin, ethylene-propylene-diene copolymer resin and similar ter-polymer resin, methylpent ene based resins or polyhutadiene.Preferably, polyolefin resin of the present invention comprises polyvinyl resin, tactic polypropylene base resin, the polybutylene-based resin of stereospecific, stereospecific ethylene-propylene-diene copolymer resin, methylpent ene based resins or polyhutadiene.
In the present invention, polyvinyl resin comprise high density polyethylene(HDPE), medium-density polyethylene, Low Density Polyethylene, linear low density of polyethylene and have at least 50wt%, especially at least 70% the ethylene copolymer of ethylene content.
In the present invention, polypropylene-based resin comprise alfon and have at least 50wt%, especially at least 70% the propylene copolymer of propylene content.
In the present invention, polybutylene-based resin comprises chevron and has the butylene copolymer of butene content of at least 50wt%, especially at least 70wt%.
In the present invention, methylpent ene based resins comprises methylpentene homopolymer and has the methylpentene copolymer of methylpentene content of at least 50wt%, especially at least 70wt%.
The comonomer that can form various above-mentioned multipolymer comprises ethene (except ethylene copolymer), propylene (except propylene copolymer), butylene (except butylene copolymer), amylene, hexene, heptene, octene, decene, undecylene, dodecylene, (methyl) acrylicacidandesters, vinyl-acetic ester and maleic anhydride.The above multipolymer can be random copolymers or segmented copolymer, and its taxis can be isotactic, also can be syndiotactic.
In general, the transparency of the polyolefin resin of nucleator of the present invention is used to be significantly improved.In addition, the present invention compared with prior art, also has following features:
(1) nucleator of the present invention adopts organic acetal and active aluminium hydroxide to carry out grafting, aluminium hydroxide and organic acetal is organically combined, improves the stability of organic acetal;
(2) smell of the acetal grafting nucleator product of the present invention's synthesis obviously reduces, and environmental-protecting performance significantly improves, and is conducive to the healthy of plastic working personnel;
(3) synthetic reaction process of the present invention is without the need to protection of inert gas, does not also need to add lower carbon number hydrocarbons as azeotropic solvent, simplifies reaction process flow process, and operate easier, economic benefit significantly improves;
(4) chemical graft nucleator of the present invention is by cheap aluminium hydroxide and organic acetal grafting, transparent modified for polyolefin plastics, and addition does not increase, and therefore the use cost of nucleator obviously reduces;
(5) 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.
Now set forth the present invention further by following examples, but be not therefore limited to following examples.
1, raw material
Raw material of the present invention is described as follows:
Homopolymerization isotactic isotactic polyprophlene resin: weight-average molecular weight 11000.
Millad3988: the third generation anti-reflection nucleating agent of Milliken company of the U.S., its chemical constitution is 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol;
YS-689/A, YS-689/B, YS-689/C, YS-689/D are respectively the nucleator prepared by the method for patent CN101613490B embodiment 1,2,5 and 7, are called YS-689 series nucleator.
Other raw materials are conventional commercial product.
2, testing method
Following methods evaluation is adopted to use the polyolefine resin composition performance of nucleator of the present invention.
Using haze meter, is the mist degree of the polyolefine resin composition of 1.0mm according to GB/T2410-1980 canonical measure thickness.Measured value is less, and transparency is better.
According to the Tc of ASTM D3418-03 standard test polyolefine resin composition.Measured value is larger, and crystal property is better.
According to the stretching yield stress of GB/T1040.2-2006 standard test polyolefine resin composition.Measured value is larger, and rigidity is better.
According to the modulus in flexure of GB/T9341-2000 standard test polyolefine resin composition.Measured value is larger, and rigidity is better.
According to the load deformation temperature (0.45MPa) of GB/T1634.2-2004 standard test polyolefine resin composition.Measured value is higher, and heat-resistant stability is better.
Embodiment 1:
The preparation of 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3methyl alcohol, stirring and dissolving.Under agitation then, add 28.3g3,4-dimethylbenzaldehyde and 1g tosic acid, 32g aluminum methylate, react 7h at 50 DEG C after, by aqueous sodium carbonate neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder samples.FT-IR test shows, sample is at 1079cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Preparation comparative example 1:
The preparation of 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbitol nucleating agent
Except not adding aluminum contained compound aluminum methylate, other conditions are identical with embodiment 1, obtain 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbitol nucleating agent.The product synthesized when not adding aluminum contained compound is called DMDBS.
Embodiment 2:
The preparation of 1,3:2,4-bis-(to methylbenzilidene) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3ethanol, stirring and dissolving.Under agitation then, add 24.6g p-tolyl aldehyde and 1.2g Phenylsulfonic acid, 43.2g aluminum ethylate, react 7h at 55 DEG C after, by calcium hydroxide aqueous solution neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder samples.FT-IR test shows, sample is at 1075cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Preparation comparative example 2:
The preparation of 1,3:2,4-bis-(to methylbenzilidene) sorbitol nucleating agent
Except not adding aluminum contained compound aluminum ethylate, other conditions are identical with embodiment 2, obtain 1,3:2,4-bis-(to methylbenzilidene) sorbitol nucleating agent.The product synthesized when not adding aluminum contained compound is called MDBS.
Embodiment 3:
The preparation of 1,3:2,4-bis-(p-chlorobenzal base) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3methyl alcohol, stirring and dissolving.Under agitation then, 26.4g 4-chloro-benzaldehyde and the 0.9g vitriol oil (concentration is 95wt%) is added, 54.4g aluminum isopropylate, react 7h at 60 DEG C after, by aqueous potassium phosphate solution neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder samples.FT-IR test shows, sample is at 1080cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 4:
The preparation of 1,3:2,4-bis-(a bromine benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3ethanol, stirring and dissolving.Under agitation then, add 37.9g 3-bromobenzaldehyde and 2.0g phosphoric acid, 65.6g trimethyl carbinol aluminium, react 7h at 70 DEG C after, by baryta water neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder samples.FT-IR test shows, sample is at 1078cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 5:
The preparation of 1,3:2,4-bis-(3,4-dimethyl benzylidene/to methylbenzilidene) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3methyl alcohol, stirring and dissolving.Under agitation then, add 13.2g3,4-dimethylbenzaldehyde and 12.3g p-tolyl aldehyde, 1.5g p-methyl benzenesulfonic acid, 15.2g aluminum methylate, after reacting 7h at 52 DEG C, by potassium hydroxide aqueous solution neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder.FT-IR test shows, sample is at 1080cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 5-1 ~ 5-5:
In embodiment 5-1 ~ 5-5, except by 3 of embodiment 5, the mol ratio of 4-dimethylbenzaldehyde/p-tolyl aldehyde replaces with following mol ratio [3,4-dimethylbenzaldehyde/p-tolyl aldehyde (mol)=4/1,3/1,1/3,1/4 and 1/5], outside, other conditions are identical with embodiment 5.Products obtained therefrom is white powder.The FT-IR spectrum test of these samples finds, each sample is all at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 6:
The preparation of 1,3:2,4-bis-(p-chlorobenzal base/to methylbenzilidene) sorbyl alcohol-aluminium hydroxide grafting nucleator
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3virahol, stirring and dissolving.Under agitation then, 17.6g 4-chloro-benzaldehyde and 8.2g p-tolyl aldehyde is added, 1.8g Phenylsulfonic acid, 40g aluminium butoxide, react 7h at 75 DEG C after, by potassium hydroxide aqueous solution neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder.FT-IR test shows, sample is at 1075cm
-1there is very strong Al-O key infrared absorption peak in place, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 6-1 ~ 6-4:
In embodiment 6-1 ~ 6-4, mol ratio except the 4-chloro-benzaldehyde/p-tolyl aldehyde by embodiment 6 replaces with following mol ratio [4-chloro-benzaldehyde/p-tolyl aldehyde (mol)=3/1,4/1,1/3,1/4], outside, other conditions are identical with embodiment 6.Products obtained therefrom is white powder.The FT-IR spectrum test of these samples finds, each sample is all at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 7:
Take aluminum chloride as the preparation of 1,3:2,4-bis-(3, the 4-dimethyl benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator in aluminium source
In four mouthfuls of reactors that agitator, feed hopper, thermometer and condenser are housed, add 18.2g sorbyl alcohol, 100cm
3methyl alcohol, stirring and dissolving.Under agitation then, add 28.3g3,4-dimethylbenzaldehyde and 1g tosic acid, 17.5g aluminum chloride, react 6h at 50 DEG C after, by sodium bicarbonate aqueous solution neutralization reaction system, make its pH >=10, add tap water, filtration, dry white powder.The FT-IR test of sample shows, sample is at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 8:
Take aluminum hydride as the preparation of 1,3:2,4-bis-(3, the 4-dimethyl benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator in aluminium source
Except replacing with except 15g aluminum hydride by 17.5g aluminum chloride, all the other conditions are identical with embodiment 7, the sample obtained after aftertreatment.The FT-IR test of sample shows, sample is at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 9:
Take aluminum hydride as the preparation of 1,3:2,4-bis-(3, the 4-dimethyl benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator in aluminium source
Except replacing with except 5g aluminum hydride by 17.5g aluminum chloride, all the other conditions are identical with embodiment 7, after aftertreatment, obtain sample.The FT-IR test of sample shows, sample is at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 10:
Take triethyl aluminum as the preparation of 1,3:2,4-bis-(3, the 4-dimethyl benzylidene) sorbyl alcohol-aluminium hydroxide grafting nucleator in aluminium source
Except replacing with except 29g triethyl aluminum by 17.5g aluminum chloride, all the other conditions are identical with embodiment 7, after aftertreatment, obtain sample.The FT-IR test of these samples shows, sample is at 1080cm
-1the Al-O key infrared absorption peak that neighbouring appearance is very strong, shows that active aluminium hydroxide and sorbyl alcohol hydroxyl there occurs effective graft reaction.
Embodiment 11-14 and comparative example 1-6:
The preparation of polyolefine resin composition and test
Nucleator of the present invention or existing nucleator is added by the addition in table 1 in the homopolymerization isotactic isotactic polyprophlene resin of 100 mass parts, by both Homogeneous phase mixing in stirrer, then by mixture melt kneading, at 220 DEG C, granulation, compressing tablet is carried out.
Adopt aforementioned test method to carry out performance test, list in table 1.
Table 1
The result of table 1 shows, when the nucleator of addition lower than comparative example, nucleator of the present invention is used for polyolefinic nucleation modification, and the properties of gained polyolefine resin composition comprises the transparency, rigidity and thermal characteristics and is obviously better than existing nucleator.
Comparative example 3-6
Aluminium hydroxide and DMDBS are carried out uniform physical mixed and form mixture by the mass percent that the aluminium hydroxide provided by table 2 accounts for DMDBS, using these mixtures as nucleator, and add in homopolymerization isotactic isotactic polyprophlene resin with the addition of 2.2wt ‰, carry out preparation and the test of polyolefine resin composition according to the method for embodiment 14, properties lists in table 2.
Table 2
The data of table 2 show, aluminium hydroxide and DMDBS physics compound to polyacrylic modified effect, all not as good as the modified effect of nucleator of the present invention (polyvalent alcohol two acetals-aluminium hydroxide grafts) in load deformation temperature, modulus in flexure, stretching yield stress etc.
Comparative example 7-10
Nucleator is prepared according to the method for the embodiment 1,2,5 and 7 of patent CN101613490B, be designated as YS-689/A, YS-689/B, YS-689/C, YS-689/D respectively, and add in homopolymerization isotactic isotactic polyprophlene resin with the addition of 2.2wt ‰, carry out preparation and the test of polyolefine resin composition according to the method for embodiment 14, properties lists in table 3.
Table 3
The result of table 3 shows, when addition is identical, the improvement effect of YS-689 series Nucleating Agent on Pp mist degree, compared with nucleator of the present invention, differs greatly.
Claims (10)
1. a nucleator, is characterized in that, described nucleator is for having the polyvalent alcohol two acetals-aluminium hydroxide 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. nucleator according to claim 1, is characterized in that, described C
1-C
6alkyl is methyl or ethyl; Described C
1-C
6alkoxyl group is methoxy or ethoxy; Be fluorine, chlorine or bromine with described halogen.
3. nucleator according to claim 1, is characterized in that, described polyvalent alcohol two acetal is two acetals of two acetals of sorbyl alcohol, two acetals of Xylitol or glucose.
4. nucleator according to claim 1, is characterized in that, described polyvalent alcohol two acetal is: 1,3:2,4-bis-(3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-bis-(to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-(to ethylbenzylidene/3,4-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-(to methylbenzilidene/to ethylbenzylidene) sorbyl alcohol, 1,3:2,4-bis-(benzylidene) sorbyl alcohol, 1,3:2,4-bis-(p-chlorobenzal base) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/to methylbenzilidene) sorbyl alcohol, 1,3:2,4-(p-chlorobenzal base/3,4 dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-bis-(a bromine benzylidene) sorbyl alcohol, 1,3:2,4-(3,4-dimethyl benzylidene/benzylidene) sorbyl alcohol, the arbitrary composition of 1,3:2,4-(a p-chlorobenzal base/bromine benzylidene) sorbyl alcohol or above-mentioned polyvalent alcohol two acetal.
5. a preparation method for the nucleator described in any one of Claims 1 to 4, is characterized in that, said method comprising the steps of:
In the reactor under agitation condition, polyvalent alcohol is added in organic solvent and dissolves, then aromatic aldehyde is added, add catalyzer and aluminum contained compound more afterwards, reaction 2 ~ 10 hours at room temperature ~ 80 DEG C, finally add the solution containing basic cpd, make pH >=10 of reaction system with termination reaction, namely obtain described nucleator through aftertreatment.
6. method according to claim 5, is characterized in that, the mol ratio of described aromatic aldehyde and polyvalent alcohol is 1:1.85 ~ 1:2.15.
7. method according to claim 5, is characterized in that, described organic solvent is selected from one or more of alcohol, ether or hydrochloric ether.
8. method according to claim 5, is characterized in that, described organic solvent is selected from methyl alcohol, ethanol, Virahol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, methylene dichloride, chloroform or their any mixture.
9. method according to claim 5, is characterized in that, described catalyzer is sulfuric acid, hydrochloric acid, Phenylsulfonic acid, toluene sulfonic acide, trichoroacetic acid(TCA) or trifluoroacetic acid; Be aluminium alcoholates, aluminum alkyls, the halogenide of aluminium or aluminium hydroxide with described aluminum contained compound.
10. method according to claim 5, is characterized in that, described basic cpd is the oxyhydroxide of sodium, potassium, rubidium, caesium, calcium or barium, soluble carbonate salt, supercarbonate or soluble phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410160385.8A CN104211985B (en) | 2013-10-31 | 2014-04-21 | Aluminum hydroxide-containing nucleating agent and preparation method thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013105305849 | 2013-10-31 | ||
| CN201310530584 | 2013-10-31 | ||
| CN201310530584.9 | 2013-10-31 | ||
| CN201410160385.8A CN104211985B (en) | 2013-10-31 | 2014-04-21 | Aluminum hydroxide-containing nucleating agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104211985A true CN104211985A (en) | 2014-12-17 |
| CN104211985B CN104211985B (en) | 2017-05-17 |
Family
ID=52093914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410160385.8A Active CN104211985B (en) | 2013-10-31 | 2014-04-21 | Aluminum hydroxide-containing nucleating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104211985B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629354A (en) * | 2015-03-10 | 2015-05-20 | 绍兴佳华高分子材料股份有限公司 | Nucleation lubricant for nylon and preparation method of nucleation lubricant |
| CN107236301A (en) * | 2017-06-26 | 2017-10-10 | 苏州市慧通塑胶有限公司 | PPS PC short glass fiber high molecule alloy materials and preparation method thereof |
| CN112759793A (en) * | 2021-01-25 | 2021-05-07 | 湖北新南化科技有限公司 | Chemical graft, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270209B1 (en) * | 1999-03-19 | 2001-08-07 | Canon Kabushiki Kaisha | Ink tank |
| CN101434607A (en) * | 2008-12-12 | 2009-05-20 | 深圳大学 | Method for synthesizing polyolefin nucleating agent aldehyde alcohol compound |
| CN101613490A (en) * | 2009-08-03 | 2009-12-30 | 中国石油化工股份有限公司 | A kind of polyolefin resin nucleating agent and preparation method thereof |
| CN102250398A (en) * | 2010-05-18 | 2011-11-23 | 中国石油天然气股份有限公司 | Polyolefine nucleating agent and preparation as well as application thereof |
-
2014
- 2014-04-21 CN CN201410160385.8A patent/CN104211985B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270209B1 (en) * | 1999-03-19 | 2001-08-07 | Canon Kabushiki Kaisha | Ink tank |
| CN101434607A (en) * | 2008-12-12 | 2009-05-20 | 深圳大学 | Method for synthesizing polyolefin nucleating agent aldehyde alcohol compound |
| CN101613490A (en) * | 2009-08-03 | 2009-12-30 | 中国石油化工股份有限公司 | A kind of polyolefin resin nucleating agent and preparation method thereof |
| CN102250398A (en) * | 2010-05-18 | 2011-11-23 | 中国石油天然气股份有限公司 | Polyolefine nucleating agent and preparation as well as application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629354A (en) * | 2015-03-10 | 2015-05-20 | 绍兴佳华高分子材料股份有限公司 | Nucleation lubricant for nylon and preparation method of nucleation lubricant |
| CN107236301A (en) * | 2017-06-26 | 2017-10-10 | 苏州市慧通塑胶有限公司 | PPS PC short glass fiber high molecule alloy materials and preparation method thereof |
| CN112759793A (en) * | 2021-01-25 | 2021-05-07 | 湖北新南化科技有限公司 | Chemical graft, preparation method and application thereof |
| CN112759793B (en) * | 2021-01-25 | 2021-09-03 | 湖北新南化科技有限公司 | Chemical graft, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104211985B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101613490B (en) | Polyolefin resin nucleating agent and preparation method thereof | |
| CN101987891B (en) | Polyolefin resin and nucleating agent-containing composition | |
| CN1984949B (en) | Method of nucleating a polyolefin composition with acetal-based compounds | |
| Scott et al. | Clean, efficient syntheses of cyclotriveratrylene (CTV) and tris-(O-allyl) CTV in an ionic liquid | |
| CN103319706A (en) | Polycarbonate resins and processes for producing the same | |
| CN104211985A (en) | Aluminum hydroxide-containing nucleating agent and preparation method thereof | |
| CN104163938A (en) | Nucleating agent and preparation method thereof | |
| CN106795326B (en) | A kind of transparent nucleater composition comprising three acetal of sorbierite and monoacetal | |
| CN110818543A (en) | Novel method for efficiently synthesizing dibenzoyl methane | |
| CN109369957A (en) | It is a kind of to have both UV absorption and fire-retardant difunctional phosphorus flame retardant and preparation and application | |
| George et al. | Sodium carbonate catalyzed aminolytic degradation of PET | |
| CN107382718A (en) | The method of the mesoporous alkaline molecular sieve catalyzed alcoholysis PLAs of CaO/MCF | |
| CA1092612A (en) | Method for the production of 2,4,6-tri-(3,5- ditertiary butyl-4-hydroxybenzyl) mesitylene | |
| CN104163984B (en) | A kind of polyolefine resin composition and preparation method thereof | |
| CN103087073B (en) | Preparation method of polyolefin resin nucleating agent | |
| CN104151606B (en) | Polysilsesquioxane-modified sorbitol polypropylene nucleating agent and preparation method thereof | |
| CN104194111A (en) | A polyolefin resin composition containing a nucleating agent and a preparing method thereof | |
| CN102250398B (en) | Polyolefine nucleating agent and preparation as well as application thereof | |
| CN108191882A (en) | A kind of preparation method of polyol acetal class compound | |
| CN106674122A (en) | Preparation method of 5-p-hydroxyphenyl hydantoin | |
| CN100526319C (en) | Organic phosphate rare earth salt nucleater, synthesis method and application thereof | |
| CN103415523A (en) | Process for preparing alditol acetals | |
| CA2037576C (en) | Clarifiers for polyolefins and polyolefin compositions containing same | |
| CN101007762A (en) | Method for synthesizing acetyl tributyl citrate from ketene | |
| CN102001991B (en) | Method for preparing light stabilizer (4-n-butoxy-2,2,6,6-tetramethylpiperidine) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |