CN101137722A - Polymeric lubricant having multi layer structure and manufacturing method thereof - Google Patents
Polymeric lubricant having multi layer structure and manufacturing method thereof Download PDFInfo
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- CN101137722A CN101137722A CNA2006800077539A CN200680007753A CN101137722A CN 101137722 A CN101137722 A CN 101137722A CN A2006800077539 A CNA2006800077539 A CN A2006800077539A CN 200680007753 A CN200680007753 A CN 200680007753A CN 101137722 A CN101137722 A CN 101137722A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
Disclosed are a polymeric lubricant having multi layer structure as a processing aid capable of being used to improve processability of a vinyl chloride resin, and a manufacturing method thereof. The polymeric lubricant having multi layer structure according to the present invention is provided in the form of powder, and has an excellent ability to prevent its adhesion to a metal surface upon its processing so as to give a long-term workability to an extrusion, a calendering, a blow molding, an injection molding, etc. if an small amount of the powder of the present invention is mixed with a vinyl chloride resin. Also, the processing aid of the present invention has good powder properties such as the high-temperature drying and the easy mass-production since it has an excellent flowability at high temperature. The processing aid of the present invention is provided in the form of powder through coagulation, dehydration and dry processes after a silicone-based polymer is used as a seed to manufacture a core-shell copolymer latex. Accordingly, the present invention provides a polymeric lubricant capable of controlling compatibility with the vinyl chloride resin, an important factor of the polymeric lubricant functions, and minimizing the adhesive property to a metal surface of a processing machine when a vinyl chloride resin is processed with a polymer including silicone-based polymer. And, the present invention may provide a polymeric powder having powder properties, which may easily form a core-shell structure and be dried at the high temperature and conveniently mass-produced since a silicone-based polymer is introduced when the polymeric lubricant is manufactured according to the method of the present invention.
Description
Technical field
The present invention relates to a kind of polymeric lubricant and preparation method thereof with multilayered structure.More specifically, the present invention relates to polymeric lubricant that has by multilayered structure and preparation method thereof, this lubricant is with the Acrylic Acid Monomer of emulsion, main amount with based on aromatic vinyl monomer and a small amount of siloxanes polymeric blends, to have with preparation after the latex of nucleocapsid structure as crystal seed based on the polymkeric substance of siloxanes by polymerization, by condense, dehydration and drying process provide with the polymeric powder form.
Background technology
Polymeric lubricant with multilayered structure according to the present invention does not influence the inherent physicals of vinyl chloride resin, and makes the lip-deep adhesivity of its processor of processing is minimized.It provides with powder type, and is included in the polyvinyl chloride (PVC) RESINS.In addition, owing at high temperature have excellent flowing according to polymeric lubricant of the present invention, so it has and for example is easy to mass-produced powder property.And, polymeric lubricant with multilayered structure according to the present invention has and prevents that it from adhering to the excellent performance to its metallic surface that processes, if so that a small amount of powder of the present invention is mixed with polyvinyl chloride (PVC) RESINS, extrude giving, the secular workability of calendering, blowing, injection moulding etc.
Polyvinyl chloride (PVC) RESINS has been widely used in multiple field, has the fabulous physics and the moulded piece of chemical property because it can provide.But, there is multiple processing problems in polyvinyl chloride: because its processing temperature approaches heat decomposition temperature, therefore have narrower moldable temperature range, high melting temperature (Tm) and low melt flow, and be easy to form settling, therefore ought at high temperature add man-hour to it, because its trend adheres to the metallic surface of processor, make the quality deterioration of the finished product.
Known addressing the above problem is particularly to the multiple technologies of the adhesion property of processor surface metal.Representational technology is for example used a kind of copolymerization polymeric lubricant, and this copolymerization polymeric lubricant is included in the polyvinyl chloride (PVC) RESINS (methyl) alkyl acrylate monomer and the aromatic vinyl monomer as main component.U.S. Patent number 4,086,296 have proposed a kind of polymkeric substance of being made by the composition of low-molecular weight polymer emulsion and high-molecular weight polymer, wherein low-molecular weight polymer is with a step or a multistep, by the polypropylene acid alkyl ester, other Acrylic Acid Monomer and their the copolymerizable monomer mixture based on vinyl obtain, and high-molecular weight polymer is by going on foot or multistep further polymerization methyl methacrylate with one, acrylate, other Acrylic Acid Monomer, vinylbenzene, and their the copolymerizable monomer mixture with vinyl obtains.Zhi Bei acrylic acid composition polymkeric substance has the but also not satisfied performance that prevents to adhere to the metallic surface of suitable excellence like this, and because in drying process under the high temperature powder flowbility also made it have shortcoming by deterioration at mass production.
U.S. Patent number 5,371,149 disclose a kind of lubricant that is used for thermoplastic resin, it is a kind of three step polymkeric substance (three-stage polymer), wherein in step 1 and step 3, methyl methacrylate is introduced as principal monomer, in intermediate steps (step 2), will introduce as principal monomer by the multipolymer that alkyl acrylate and aromatic vinyl monomer are formed, but this polymkeric substance can not satisfy in the drying process powder flowbility under the high temperature and prevent to adhere to the performance of metallic surface.
U.S. Patent number 5,942,581 provide a kind of method that is used to use the methacrylate polymer with the alkyl that contains 6～24 carbon atoms, but the shortcoming of this method is: it also is difficult to satisfied prevent adhesivity and powder flowbility at high temperature.
European Patent Application No. 1209203A1 discloses a kind of thermoplastic resin processing aid that is used for, wherein the organo-peroxide that comprises t-butylperoxy by use comprises (methyl) acrylate of the Sauerstoffatom except that the ester bond of alkyl acrylate and their copolymerizable mixture of vinyl monomer as polymerization starter with copolymerization, for example can improve the adhering active long-term time length for the metallic surface.But Zhi Bei processing aid at high temperature has inadequate powder flowbility like this.
Summary of the invention
Technical problem
In order to address these problems, the purpose of this invention is to provide a kind of polymeric lubricant and preparation method thereof with multilayered structure, it is by minimizing the adhesivity to the metallic surface of processor in the vinyl chloride resin processing, and have fabulous powder flowbility, and to extrude, calendering, blowing, injection moulding etc. give fabulous long-time workability.
Technical scheme
By the polymeric lubricant with multilayered structure that contains based on the crystal seed of siloxanes is provided, realize aforementioned and/or others of the present invention.
Preferably, described polymeric lubricant comprises:
A) comprise the crystal seed based on siloxanes of 3～10 weight part seed polymer latex, described seed polymer latex by comprising 6～25 weight % the silane that contains vinyl and the mixture and the latex polymerization of the cyclosiloxane of surplus obtain;
B) comprise the nuclear of nuclear polymer that is used to cover crystal seed of 40～77 weight parts, described nuclear polymer comprise 30～60 weight % aromatic vinyl monomer, 5～15 weight % based on the comonomer of vinyl and the alkyl acrylate of surplus, and it is by obtaining with letex polymerization in the presence of crystal seed; And
C) shell polymeric that is used to apply nuclear polymer of 13～57 weight parts, described shell polymeric comprises the aromatic vinyl monomer of 1～37 weight %, the polymkeric substance based on siloxanes of 1～3 weight %, the methyl methacrylate of 60～98 weight % and the comonomer based on vinyl of surplus, and it is by obtaining with letex polymerization in the presence of nuclear polymer.
Embodiment
Hereinafter, describe the present invention with reference to preferred implementation.
Polymeric lubricant according to the present invention comprises the crystal seed based on siloxanes, and preferably comprise: comprise the crystal seed based on siloxanes of the seed polymer latex of 3～10 weight parts, described seed polymer latex by comprising 6～25 weight % the silane that contains vinyl and the mixture and the latex polymerization of the cyclosiloxane of surplus obtain; The nuclear of nuclear polymer that is used to apply crystal seed that comprises 40～77 weight parts, described nuclear polymer comprise 30～60 weight % aromatic vinyl monomer, 5～15 weight % based on the comonomer of vinyl and the alkyl acrylate of surplus, and it is by obtaining with letex polymerization in the presence of crystal seed; And the shell polymeric that is used to apply nuclear polymer of 13～57 weight parts, described shell polymeric comprises the aromatic vinyl monomer of 1～37 weight %, the polymkeric substance based on siloxanes of 1～3 weight %, the methyl methacrylate of 60～98 weight % and the comonomer based on vinyl of surplus, and it is by obtaining with letex polymerization in the presence of nuclear polymer.
Polymkeric substance based on siloxanes of the present invention can be by the material preparation of the group that is selected from the silane that comprises cyclosiloxane and comprise vinyl.
Described cyclosiloxane can be selected from the group that comprises hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, ten diformazan basic rings, six siloxanes or its mixture.
More preferably use octamethylcyclotetrasiloxane as cyclosiloxane.The described silane that comprises vinyl can be selected from the group that comprises triethoxy vinyl silanes, vinylformic acid 3-(trimethoxysilyl) propyl ester, methacrylic acid 3-(trimethoxysilyl) propyl ester or its mixture.
In the polymkeric substance based on siloxanes, the scope that the described silane that comprises vinyl can 6～25 weight % is used.If use the silane that comprises vinyl with 6 weight % or littler amount, there is the problem that can not fully prevent the adhesion property of metallic surface in so described polymkeric substance based on siloxanes; And if its content surpasses 25 weight %, because the vinyl chloride resin fusing reduces, may there be the problem with enough workabilitys in described polymkeric substance based on siloxanes so.
Nuclear polymer of the present invention can comprise aromatic vinyl monomer by being selected from, based on the material preparation of the group of the comonomer of vinyl and alkyl acrylate, and it can prepare by polymerization in the presence of the polymkeric substance based on siloxanes.
Described aromatic vinyl monomer can be vinylbenzene, alpha-methyl styrene or its mixture.
Described comonomer based on vinyl can be the monomer based on vinyl of the routine that can close with aromatic vinyl monomer and/or described alkyl acrylate copolymer, and the example of described comonomer based on vinyl comprises methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, lauryl methacrylate, the methacrylic acid stearyl, methacrylic acid tridecyl ester, the methacrylic acid isobutyl, the methacrylic acid tertiary butyl ester, methacrylic acid 2-ethylhexyl, vinyl cyanide etc., but the present invention is not restricted to this, and also can select to use the conventional commercially available monomer based on vinyl that contains at least one two key in its molecule.
Described alkyl acrylate can be selected from and comprise for example group of the alkyl acrylate with the alkyl that contains 2～8 carbon atoms of ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, 2-EHA, Octyl acrylate or its mixture.Described alkyl acrylate can be preferably selected from the group that comprises butyl acrylate, 2-EHA and ethyl propenoate with low relatively second-order transition temperature.
In described nuclear polymer, the amount that described aromatic vinyl monomer can 30～60 weight % is used.If use aromatic vinyl monomer with 30 weight % or littler amount, may there be the problem with the disengaging performance degradation of metallic surface in then described nuclear polymer; And if its content surpasses 60 weight %, the problem that it may exist the consistency with polyvinyl chloride to reduce.Use based on the amount that the comonomer of vinyl can 5～15 weight %.If described comonomer based on vinyl uses with 5 weight % or littler amount, the problem that described nuclear polymer may exist the consistency with polyvinyl chloride to reduce; And if its content surpasses 15 weight %, it may exist in the problem of lubricant properties deterioration in its processing.Described alkyl acrylate can be used as the aromatic vinyl monomer of use and uses based on the residuum of the comonomer of vinyl.
Shell polymeric of the present invention can comprise aromatic vinyl monomer, the material preparation based on the group of the comonomer of vinyl of polymkeric substance, methyl methacrylate and surplus based on siloxanes by being selected from, and it can prepare by polymerization in the presence of nuclear polymer latex.
Described aromatic vinyl monomer can be identical or similar with the material that is used to prepare nuclear polymer latex.
Described polymkeric substance based on siloxanes can be identical or similar with the material that is used to prepare crystal seed.
Described comonomer based on vinyl also can be identical or similar with the material that is used to prepare nuclear polymer.
In described shell polymeric, the amount that described aromatic vinyl monomer can 1～37 weight % is used.If described aromatic vinyl monomer uses with 1 weight % or littler amount, there is the problem that has reduced to prevent to adhere to the ability of metallic surface in then described shell polymeric; And if its content surpasses 37 weight %, because the consistency of itself and polyvinyl chloride, there is the problem of surface property deterioration in it.Described polymkeric substance based on siloxanes can 1～3 weight % amount use.If described polymkeric substance based on siloxanes uses with 1 weight % or littler amount, described shell polymeric is present under the high temperature powder property does not have improved problem; And if its content surpasses 3 weight %, it exists in the problem that melt flow significantly reduces in its processing.Described comonomer based on vinyl can be used as the aromatic vinyl monomer of use and uses based on the residuum of the comonomer of vinyl.
Described seed polymer latex can use based on the amount of 3～10 weight parts of the total amount of polymeric lubricant, and preferred 5～8 weight parts.If described seed polymer latex uses with 3 weight parts or littler amount, then problem is, prevents that its ability that adheres to the metallic surface from can significantly be reduced; And if described seed polymer latex uses with 10 weight parts or bigger amount, melt flow can reduce with the amount that joins polyvinyl chloride (PVC) RESINS.
Described nuclear polymer can use based on the amount of 40～77 weight parts of polymeric lubricant total amount.If described nuclear polymer uses with 40 weight parts or littler amount, then problem is to prevent that its ability that adheres to the metallic surface from can significantly reduce; And if described nuclear polymer uses with 77 weight parts or bigger amount, then can the deterioration drying process in powder property under high temperature.
Described shell polymeric can use based on the amount of 13～57 weight parts of polymeric lubricant total amount.If described shell polymeric uses with 13 weight parts or littler amount, then problem is, can reduce the powder flowbility under the high temperature; And if described shell polymeric uses with 57 weight parts or bigger amount, then polymeric lubricant character may deterioration.
The weight-average molecular weight of described nuclear polymer is adjusted to 5,000～300, in 000 the scope, and more preferably 10,000～200,000.If described nuclear polymer has 5,000 or littler weight-average molecular weight, then problem is to reduce powder flowbility; And if described nuclear polymer has 300,000 or bigger weight-average molecular weight, then significantly deterioration preventing its adhere to the ability of metallic surface.
The weight-average molecular weight of described shell polymeric can be adjusted in 10,000～1,000,000 the scope.If described shell polymeric has 10,000 or littler weight-average molecular weight, then problem is to reduce the flowability of powder; And if described shell polymeric has 1,000,000 or bigger weight-average molecular weight, then significantly deterioration preventing its adhere to the ability of metallic surface, and can deterioration the surface property of ripple for example.Especially, described shell polymeric can have at least 10,000 weight-average molecular weight, and also has the weight-average molecular weight higher than the weight-average molecular weight of described nuclear polymer, and (having) 1,000,000 or littler weight-average molecular weight.If the weight-average molecular weight that is produced by the mixture itself that is used for the shell reaction is lower than the weight-average molecular weight of described nuclear multipolymer, then problem is to reduce drying efficiency, and since condense, dewater and subsequently drying process in may form the agglomerate of powder, the problem that scale operation can occur being difficult to.
Because the polymkeric substance based on siloxanes is used as crystal seed, suitably regulate the content of nuclear and shell, and in shell, use a small amount of polymkeric substance based on siloxanes, therefore the polymeric lubricant with multilayered structure according to the present invention at high temperature has fabulous powder flowbility and prevent fabulous effect for the adhesion property of the metallic surface of processor in the process of processing vinyl chloride resin.
Described polymeric lubricant can be by using based on the polymkeric substance of siloxanes and have monomer with the low consistency in metallic surface, and give powder flowbility and prepare.The flowability of described polymeric lubricant is guaranteed by second-order transition temperature and the molecular weight of regulating nuclear and shell.This polymeric lubricant is owing to have lower glass transition temperatures, and it is difficult to separate with form of powder.
In order to address this problem, in nucleocapsid structure during the polymerization shell, by using the monomer that has high glass-transition temperature on a small quantity and, can developing polymkeric substance based on siloxanes with fabulous powder property on a small quantity based on the polymkeric substance of siloxanes.That is to say, by by the monomer with high glass-transition temperature and a certain amount of shell of forming based on the polymkeric substance of siloxanes with by using based on the polymkeric substance of siloxanes and having second-order transition temperature is adjusted to the polymerization of the low-level polymeric lubricant for preparing (nuclear) with the monomer of the low consistency of metallic surface, have fabulous powder flowbility and prevent polymeric powder admirably and in condense technology and drying process afterwards, make for the effect of the adhesion property of metallic surface.
Polymeric lubricant of the present invention (nuclear) has reduced the adhesivity to the metallic surface of processor by reducing the affinity of molten resin to the metallic surface.And, improve interparticle slippage by the reaction between the polyvinyl chloride (PVC) RESINS particle.This effect has reduced frictional force and has postponed gelation.This effect also reduced by processing cause heat gain, and postponed the gelation of vinyl chloride resin.Before gelation is carried out fully, this effect appears in the starting stage of processing, and because heat in the course of processing and friction, polyvinyl chloride (PVC) RESINS is melted.That is to say that described polymeric lubricant plays the effect of the exterior lubricant that is used for its processing.Therefore, implement preparation polymeric lubricant (nuclear) in order and prevent step for the adhesion property effect of metallic surface with improvement, and preparation polymkeric substance (shell) is obtained according to polymeric lubricant of the present invention in identical reactor by the multilayer latex with nucleocapsid structure to promote the step of preparation polymeric lubricant in commercial production.
By after preparing polymeric lubricant of the present invention with letex polymerization with the latex form, by condense, dehydration and drying process, obtain the polymeric lubricant of the present invention of powder type.
Because its excellent flowing at high temperature, the polymeric lubricant with multilayered structure of the present invention is useful to scale operation.In addition, owing to add with the amount based on 0.1～5 weight part of the vinyl chloride resin of 100 weight parts, the polymeric lubricant with multilayered structure of the present invention has and prevents for the good action of the adhesion property of the metallic surface of processor and can the deterioration vinyl chloride resin composition not shown intrinsic physics and the chemical property that goes out.
And, below will describe the above-mentioned preparation method with polymeric lubricant of multilayered structure of the present invention in detail.
Preparing the method with polymeric lubricant of multilayered structure of the present invention comprises:
A) mixture that is used to form crystal seed that comprises the cyclosiloxane of the silane that comprises vinyl of 6～25 weight % and surplus by polymerization prepares the step of seed latex;
B) in the abovementioned steps that comprises 3～10 weight parts, obtain based in the presence of the seed latex of the polymkeric substance of siloxanes, the mixture that is used to form nuclear based on the alkyl acrylate of the comonomer of vinyl and surplus that comprises aromatic vinyl monomer, 5～15 weight % of 30～60 weight % by polymerization, preparation are used to cover the step of the nuclear polymer of seed polymer; And
In the presence of the nuclear polymer of the seed polymer of 3～10 weight parts that c) in comprising abovementioned steps, obtain and the nuclear polymer of 40～77 weight parts, the mixture that is used to form shell based on the comonomer of vinyl that comprises the methyl methacrylate of the multipolymer based on siloxanes, 60～98 weight % of aromatic vinyl monomer, 1～3 weight % of 1～37 weight % and surplus by polymerization, preparation are used to cover the step of the shell polymeric latex of nuclear polymer.
Should be appreciated that the various compositions that constitute polymeric lubricant are identical with the composition that is used to describe the aforementioned polymeric lubricant of formation.
In the step of the seed latex of preparation process in a), except that aforementioned composition, emulsifying agent can be added so that composition emulsification, can use and have 10, the homogenizer of 000rpm rotary power is ground to the fine particle size with emulsified monomer, the mixture that generates can be joined in the acidic aqueous solution of heat with polymerization, cooling, then with the alkaline aqueous solution neutralization with the polymer latex of preparation based on siloxanes.
In addition, in the step based on the polymer seed of siloxanes of preparation process in a), can add catalyzer and emulsifying agent.
Described catalyzer is preferably Witco 1298 Soft Acid, and Phenylsulfonic acid that it replaces for aliphatics and the Sodium dodecylbenzene sulfonate etc. that uses the Witco 1298 Soft Acid that sodium replaces are as emulsifying agent.After finishing polyreaction, can use yellow soda ash is 7～8 in order to acid latex is neutralized to the pH value.
At preparation process b) in the step of nuclear polymer in, except that aforementioned composition, can be sequentially added into chain-transfer agent, polymerization starter, emulsifying agent and ion exchanged water, perhaps the form with pre-emulsion adds in order or simultaneously with the preparation copolymer emulsion.
At preparation process c) in the step of shell polymer latex in, except that aforementioned composition, can add chain initiator, polymerization starter, emulsifying agent and ion exchanged water simultaneously, perhaps simultaneously or be sequentially added into the preparation copolymer emulsion with the form of pre-emulsion.
Can use known emulsifying agent as the emulsifying agent that can be used for above-mentioned reaction, but be not restricted to this.For example, described emulsifying agent comprises the anionic emulsifier as soap, alkyl sulfonic ester salt, alkylbenzene sulfonate, sulfo-succinic acid diester salt, perhaps as the nonionic emulsifying agent of polyoxyethylene groups alkyl oxide, polyoxyethylene groups fatty acid ester etc., and they can separately or be used in combination.
Can use conducts such as water-soluble or fat-soluble initiators, redox initiator can be used for the initiator of this reaction.The example of organo-peroxide comprises tertbutanol peroxide, cumene hydroperoxide, benzoyl peroxide, laurylperoxide etc.And water soluble starter comprises Potassium Persulphate, ammonium persulphate, Sodium Persulfate etc.
The chain-transfer agent that is used for this reaction is not restricted to this.For example, can use uncle's lauryl mercaptan, n-dodecyl mercaptan etc.
As previously discussed, when will be with condense de-watering of slurries that polymeric latex obtained and when dry of calcium chloride, because it has fabulous powder flowbility, the polymerized emulsion with multilayered structure prepared in accordance with the present invention has powder property to carry out conventional scale operation.And, Powdered polymeric lubricant of the present invention with multilayered structure have prevent for roll, extrude, the fabulous effect of the metallic surface adhesion property of processor in blowing, Shooting Technique etc., therefore it is joined polyvinyl chloride (PVC) RESINS, can improve its processing throughput.
Hereinafter, only provided detailed description of the present invention and the specific embodiment that preferred implementation of the present invention is described, and can not make the spirit and scope of the invention be limited to following preferred implementation with illustrational hairdo.
(preparation of powder)
Add the solids component of the calcium chloride (10 weight %) of 4 weight parts as the polymer latex Ruzhong, condensation is to obtain slurry, and by with this slurry of ion-exchange water washing 2～3 times, remove for example resistates of metal ion etc., and dewater, then with the small-sized fluidized bed moisture eliminator that is used for laboratory applications under 50 ℃, to the slurry through dehydration carry out 4 hours dry to obtain powdered sample.
(weight-average molecular weight)
The sample dissolution that will be obtained by the method for generation powder uses GPC to measure the dissolving part in THF then.In working curve, use the polystyrene standard sample.
(powder flowbility)
The sample that obtained by the method for preparing powder was flowed 30 minutes in 75 ℃ at the small-sized fluidized bed moisture eliminator that is used for laboratory applications, measure the caking level of powder then.Use 5 grades of method methods to assess, and its standard is as follows.
5: sample powder does not have caking fully.
4: sample powder is almost lumpd.
The sample powder caking of 3:1/4.
The sample powder caking of 2:1/2.
1: at least 3/4 sample powder caking.
(adhesion property)
In order to measure adhesion property, at ambient temperature with the polyvinyl chloride (polymerization degree=800 of 100 weight parts, LS-080, make by LG chemistry company limited), 3.0 weight parts join kneader (Henshel Mixer) based on the stablizer of tin and the calcium stearate (Ca-St) of 0.9 weight part, with 1,000rpm mixes, and elevated temperature to 115 ℃ is cooled to 40 ℃ then to form masterbatch simultaneously.
The sample of 3.0 weight parts is joined in the masterbatch, mix once more at ambient temperature, use 6 in2 roller mills under the condition of the roller revolution of 200 ℃ mixing temperature, 14 * 15rpm and 0.3mm roll gap, to grind 100 weight part powdered mixture 4 minutes, then in roller surface measurements adhesion property.Use 5 grades of methods to assess, and its standard is as follows.
5: do not have extension (extend) fully with its peel sample powder.
4: almost extend with its peel sample powder.
3: extend slightly with its peel sample powder.
2: obviously extend with its peel sample powder.
1: sample powder is peeled off fully.
(gelation time)
Use the Haake rheometer under the condition of 180 ℃ and 30rpm, the time cycle from minimum load to maximum load is measured in the poly (vinyl chloride) resin composition mixing that 60 weight parts are identical with being used for the adhesion property assessment then.
(optical property)
Use 2 roller mills in 200 ℃ of grindings be used to measure the identical poly (vinyl chloride) resin composition of adhesion property 4 minutes, to obtain the sheet of 0.4mm.This sheet is cut into 150mm * 200mm, and be laminated on the mould of 3mm * 170mm * 220mm with identical grinding direction.Use 195 ℃ hot pressing that this laminate was exerted pressure 8 minutes, be used to measure the thick sample of 3mm of transparency and turbidity (haze) with preparation.
Embodiment
In the following example and Comparative Examples, used identical polymer seed latex based on siloxanes.The method for preparing crystal seed is as follows.
(based on the preparation of the polymer seed latex of siloxanes)
235g ion exchanged water, 1g Witco 1298 Soft Acid (70 weight % solution), 5g Sodium dodecylbenzene sulfonate (9.5 weight % solution), 71.5g prestox ring tetrasilane, 3.5g triethoxy methyl silicane and 6.5g methacrylic acid trimethoxysilyl propyl ester are added in the container to carry out emulsification, and use homogenizer with 10, the high speed rotating power of 000rpm grinds 30 seconds to reach the fine particle size.Emulsified monomer is added reactor under nitrogen atmosphere, and when the temperature that is heated to 85 ℃, reacted 5 hours.Finishing reaction, monomer is cooled to envrionment temperature, and kept 24 hours, is 7.5 by being neutralized to the pH value with yellow soda ash (2 weight % solution) then, the preparation seed latex.Polymeric latex has 1,500
Size of particles and 85% turnover ratio.
Embodiment 1
1) reactions steps 1: the nuclear polyreaction
The polymer seed latex based on siloxanes of 139.66 weight parts is joined in the 3L4 neck reactor that disposes thermometer, nitrogen syringe, water cooler and agitator, then to wherein adding the 261.3g ion exchanged water.In another container, add 200g ion exchanged water, 15.6g3 weight % sodium laurylsulfonate (sodium lauryl sulphate, SLS) solution, 150.0g vinylbenzene, 126.0g butylacrylic acid ester, 30.0g methyl methacrylate, uncle's 0.1g lauryl mercaptan, and stir to prepare stable pre-emulsion.Under 75 ℃ temperature and nitrogen atmosphere, in reactor, added emulsified monomer (pre-emulsion) 3 hours continuously.At this moment, when the temperature with inside reactor remains on 75 ℃, simultaneously to potassium persulfate solution that wherein adds 0.42g3% continuously and 10g activator solution.After reaction 3 hours, the polymer latex that the mixture that generates 75 ℃ of stirrings had 50,000 weight-average molecular weight with acquisition in 1 hour.
2) reactions steps 2: the shell polyreaction
(sodium lauryl sulphate, SLS) solution, 183.36g methyl methacrylate, 75.36g vinylbenzene, uncle's 0.1g lauryl mercaptan mix with the preparation pre-emulsion with the sodium laurylsulfonate of 461.3g ion exchanged water, 15.6g3 weight %.After preparing stable pre-emulsion, preemulsion mixture and 24.58g are joined in the polymeric latex of preparation in the reactions steps 1 simultaneously based on the polymer latex of siloxanes, and to wherein adding 3.25g3% potassium persulfate solution and 10g activator solution simultaneously, then in 75 ℃ of reactions.Stir the mixture that generates had 150,000 molecular weight in 1 hour with acquisition final polymer latex.
Activator used herein is the solution that comprises 0.015 parts by weight of ethylene base diamines, four SODIUMNITRATE, 0.02 parts by weight of formaldehyde V-Brite B, 0.001 parts by weight of ferrous sulfate heptahydrate, 1.165 weight part ion exchanged waters.
Be listed in the table below in 1 preparing main component in each reactions steps of multipolymer of main component in the step of multipolymer of embodiment 1 and described subsequently preparation embodiment 2～6 and Comparative Examples 1～4 as mentioned above.
Embodiment 2
In the first step, use 223.46 weight part silicone polymer seed latex, polymerization process is identical with embodiment 1 method thereafter.
Embodiment 3
In the first step, use 83.80 weight part silicone polymer seed latex, polymerization process is identical with embodiment 1 method thereafter.
Embodiment 4
In the first step, use 279.32 weight part silicone polymer seed latex, polymerization process is identical with embodiment 1 method thereafter.
Embodiment 5
In the first step, use 139.66 weight part silicone polymer seed latex and use the silicone polymer seed latex that is used for shell of 36.87 weight parts, polymerization process is identical with embodiment 1 method thereafter.
Embodiment 6
In the first step, use 139.66 weight part silicone polymer seed latex, and use the silicone polymer seed latex that is used for shell of 12.29 weight parts, polymerization process is identical with the method for embodiment 1 thereafter.
Comparative Examples 1
In the first step, use the silicone polymer seed latex of 27.93 weight parts, polymerization process is identical with the method for embodiment 1 thereafter.
Comparative Examples 2
In the first step, use 418.98 weight part silicone polymer seed latex, polymerization process is identical with the method for embodiment 1 thereafter.
Comparative Examples 3
In the first step, use 139.66 weight part silicone polymer seed latex, and do not use the silicone polymer seed latex that is used for shell, polymerization process is identical with the method for embodiment 1 thereafter.
Comparative Examples 4
In the first step, use 139.66 weight part silicone polymer seed latex, and use the silicone polymer seed latex that is used for shell of 73.74 weight parts, polymerization process is identical with embodiment 1 thereafter.
Table 1
| Project | Composition | Molecular weight (Mw, 10,000) | ||
| Crystal seed is based on siloxanes | Nuclear | Shell MMA/ST/ is based on silicon | ||
| Polymkeric substance | MMA/ST/BA | The polymkeric substance of oxygen alkane | ||
| Embodiment 1 | 5 | 5/25/21 | 30.56/12.56/0.88 | 15 |
| Embodiment 2 | 8 | 5/23/20 | 30.56/12.56/0.88 | 14 |
| Embodiment 3 | 3 | 5/26/22 | 30.56/12.56/0.88 | 15 |
| Embodiment 4 | 10 | 5/22/19 | 30.56/12.56/0.88 | 13 |
| Embodiment 5 | 5 | 5/25/21 | 30.34/12.34/1.32 | 15 |
| Embodiment 6 | 5 | 5/25/21 | 30.78/12.78/0.44 | 15 |
| Comparative Examples 1 | 1 | 5/27/23 | 30.56/12.56/0.88 | 16 |
| Comparative Examples 2 | 15 | 5/20/16 | 30.56/12.56/0.88 | 10 |
| Comparative Examples 3 | 5 | 5/25/21 | 31/12/0 | 16 |
| Comparative Examples 4 | 5 | 5/25/21 | 29.68/11.68/2.64 | 10 |
In table 1, it is as follows to write a Chinese character in simplified form title.
ST: vinylbenzene, BA: n-butylacrylate, MMA: methyl methacrylate
Measure as embodiment that table 1 is listed and the sample of Comparative Examples are tested in order to assessment, and show the result in the table 2.
Table 2
| Project | Adhesion property | Powder flowbility | Gelation time (second) | Optical property | |
| Transparency | Turbidity | ||||
| Embodiment 1 | 5 | 4 | 130 | 73 | 26 |
| Embodiment 2 | 5 | 4 | 125 | 73 | 24 |
| Embodiment 3 | 5 | 5 | 123 | 75 | 25 |
| Embodiment 4 | 5 | 4 | 122 | 73 | 27 |
| Embodiment 5 | 5 | 4 | 135 | 72 | 30 |
| Comparative Examples 1 | 3 | 4 | 130 | 72 | 27 |
| Comparative Examples 2 | 5 | 4 | 118 | 66 | 38 |
| Comparative Examples 3 | 5 | 2 | 120 | 73 | 25 |
| Comparative Examples 4 | 5 | 5 | 140 | 69 | 35 |
With reference to the character of embodiment, the character of character of peeling off from the metallic surface and agglomeration resistance is splendid as can be seen.Under the situation of Comparative Examples 1, owing to be used for the polymer content deficiency based on siloxanes of crystal seed, adhesion property is poor; And under the situation of Comparative Examples 2 and Comparative Examples 4 since be used for crystal seed surpassed scope of the present invention, optical performance degradation based on the content of the polymkeric substance of siloxanes and the polymkeric substance that is used for every kind of shell based on siloxanes.Under the situation of Comparative Examples 3, if will not add in the shell based on the polymkeric substance of siloxanes, powder agglomates increases.As described in embodiment 1～6, as can be seen, if as crystal seed based on the amount of the polymkeric substance of siloxanes and introduce in the shell based on the amount of the polymkeric substance of siloxanes within the scope of the invention, improved sticking property and caking character and can not make optical performance degradation.
Industrial usability
Because the polymeric lubricant with multilayered structure according to the present invention has the fabulous stripping performance for the metallic surface, its can improve for extrude, the long-time workability of calendering, blowing, injection moulding etc.In addition, because its splendid stripping performance, it can carry out High-speed machining.And owing in the method for preparing polymeric lubricant of the present invention, will introduce shell based on the polymer emulsion of siloxanes, the present invention can provide the polymeric powder with good powder performance, and it can be at high temperature dry and be convenient to scale operation.
Though have illustrated and described some embodiments of the present invention, but those skilled in the art should understand that, in these embodiments, can carry out numerous modifications and variations and not depart from mechanism of the present invention and essence, and claims and the defined scope of equivalent thereof.
Claims (9)
1. polymeric lubricant with multilayered structure, this polymeric lubricant comprises: based on the crystal seed of siloxanes.
2. polymeric lubricant according to claim 1, this polymeric lubricant further comprises:
A) comprise the crystal seed based on siloxanes of 3～10 weight part seed polymer latex, the silane that contains vinyl and the mixture of the cyclosiloxane of surplus and the polymerization of latex of described seed polymer latex by comprising 6～25 weight % obtains;
B) comprise the nuclear of nuclear polymer that is used to cover crystal seed of 40～77 weight parts, described nuclear polymer comprise 30～60 weight % aromatic vinyl monomer, 5～15 weight % based on the comonomer of vinyl and the alkyl acrylate of surplus, and it is by obtaining with letex polymerization in the presence of crystal seed; And
C) shell polymeric that is used to cover nuclear polymer of 13～57 weight parts, described shell polymeric comprises the aromatic vinyl monomer of 1～37 weight %, the polymkeric substance based on siloxanes of 1～3 weight %, the methyl methacrylate of 60～98 weight % and the comonomer based on vinyl of surplus, and it is by obtaining with letex polymerization in the presence of nuclear polymer.
3. polymeric lubricant according to claim 2, wherein, described cyclosiloxane is selected from the group of being made up of hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, ten diformazan basic rings, six siloxanes.
4. polymeric lubricant according to claim 2, wherein, the described silane that contains vinyl is selected from the group of being made up of triethoxy vinyl silanes, vinylformic acid 3-(trimethoxysilyl) propyl ester, methacrylic acid 3-(trimethoxysilyl) propyl ester and composition thereof.
5. polymeric lubricant according to claim 2, wherein, described aromatic vinyl monomer is selected from the group that comprises vinylbenzene, alpha-methyl styrene and composition thereof.
6. polymeric lubricant according to claim 2, wherein, described alkyl acrylate is selected from the group of being made up of the vinylformic acid lower alkyl ester with the alkyl that contains 2～8 carbon atoms, and the vinylformic acid lower alkyl ester of the alkyl of described 2～8 carbon atoms is selected from the group of being made up of ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, 2-EHA and Octyl acrylate.
7. polymeric lubricant according to claim 2, wherein, described nuclear polymer has 5,000～300,000 weight-average molecular weight.
8. polymeric lubricant according to claim 2, wherein, described shell polymeric has 10,000～1,000,000 weight-average molecular weight.
9. polymeric lubricant according to claim 8, wherein, described shell polymeric has at least 10,000 weight-average molecular weight, and have the weight-average molecular weight higher than the weight-average molecular weight of nuclear polymer, and have 1,000,000 or littler weight-average molecular weight.
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| KR1020050048358 | 2005-06-07 | ||
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| KR20050107638 | 2005-11-10 | ||
| KR1020050107638 | 2005-11-10 | ||
| PCT/KR2006/001005 WO2006132471A1 (en) | 2005-06-07 | 2006-03-20 | Polymeric lubricant having multi layer structure and manufacturing method thereof |
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| CN101869939A (en) * | 2009-04-22 | 2010-10-27 | 通用汽车环球科技运作公司 | Improve solid lubricant films tribological property and the adhering method that is attached to heat-formable material |
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| KR101591565B1 (en) * | 2013-04-23 | 2016-02-03 | 주식회사 엘지화학 | Acrylic lubricant, method for preparing latex powder, and vinyl based resin composition |
| KR102006725B1 (en) * | 2016-06-14 | 2019-08-02 | 주식회사 엘지화학 | Acrylic processing aid and vinyl chloride resin composition comprising the same |
| KR102093964B1 (en) | 2016-08-09 | 2020-03-26 | 주식회사 엘지화학 | Acrylic processing aid and vinyl chloride resin composition comprising the same |
| KR102067870B1 (en) * | 2017-03-20 | 2020-01-17 | (주)엘지하우시스 | Poly vinyl chloride resin composition and poly vinyl chloride film therefrom |
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| JP3288185B2 (en) * | 1994-10-07 | 2002-06-04 | 日立化成工業株式会社 | Epoxy resin molding material for sealing electronic parts and semiconductor device using the same |
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| CN101869939A (en) * | 2009-04-22 | 2010-10-27 | 通用汽车环球科技运作公司 | Improve solid lubricant films tribological property and the adhering method that is attached to heat-formable material |
| CN101869939B (en) * | 2009-04-22 | 2012-11-21 | 通用汽车环球科技运作公司 | Method to improve solid lubricant film tribological performance and adhesion to hot forming material |
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