CN114381078A - Processing aid for thermoplastic polymer and melt-processable composition containing same - Google Patents
Processing aid for thermoplastic polymer and melt-processable composition containing same Download PDFInfo
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- CN114381078A CN114381078A CN202210056451.1A CN202210056451A CN114381078A CN 114381078 A CN114381078 A CN 114381078A CN 202210056451 A CN202210056451 A CN 202210056451A CN 114381078 A CN114381078 A CN 114381078A
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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Abstract
The present invention provides a processing aid for thermoplastic polymers and melt processable compositions comprising the same; the processing aid comprises the following components in percentage by weight: 10-70 wt% of polyalkylacrylate, and the balance of fluoropolymer; wherein the weight average molecular weight of the polyalkylacrylate is greater than 15 ten thousand. The processing aid for the thermoplastic polymer is added with the polyalkylacrylate as a synergist, so that the content of the fluorine-containing polymer can be reduced, and the use effect of the processing aid is maintained or even improved; in addition, the price of the polyalkyl acrylate is only 20-30% of that of the fluorine-containing polymer, so that the cost of the processing aid can be greatly reduced.
Description
Technical Field
The invention belongs to the technical field of modification aids for processing thermoplastic polymers, and particularly relates to a processing aid for a thermoplastic polymer and a melt-processable composition containing the processing aid.
Background
A common processing method for polymer materials is to feed a thermoplastic polymer into a screw extruder, through different types of dies, and finally to cool it into a product having the shape of the die. For example, the polyolefin-based polymer melt is extruded through a screw extruder to be processed into a pipe, a cable sheath, a film, or the like by this method.
In order to increase the production efficiency and reduce the production cost, the screw rotation speed of the extruder is usually increased to increase the extrusion speed, but the higher the extrusion speed, the higher the shear rate of the polymer melt. For any melt-processable thermoplastic polymer composition, there is a critical value of shear rate below which the extrudate surface is smooth, but above which the extrudate surface becomes rough, a condition commonly referred to as melt fracture. Initial melt fracture manifests itself as a "sharkskin" phenomenon, i.e., loss of surface gloss; it is again seriously represented by ridges transverse to the direction of extrusion, i.e. annular threads appearing on the surface of the extrudate; it is more seriously manifested by the phenomenon of "continuous melt fracture", i.e. severe deformation of the extrudate surface into irregular shapes. However, high speed extrusion at high efficiency and low cost must be optimized in contrast to low shear rates to avoid melt fracture.
As early as 1964, U.S. Pat. No.3125547 discloses a fluoropolymer as a processing aid for improving the processability of polyolefin-based polymers, and compared with the conventional method of reducing the extrusion speed, increasing the processing temperature, changing the die shape or adding a low-molecular-weight lubricant, the content of the fluoropolymer in the polyolefin-based polymers is about 500ppm, so that the problem of shark skin on the surface of an extrudate can be effectively solved, and the physical properties of the polyolefin-based polymers are not affected.
There have been subsequent related art and patents on improving the processing of polyolefin-based polymers worldwide, such as U.S. patent No.5397897 to Morgan et al, discloses a fluoroelastomer, U.S. patent No.5464904 to Chapman et al, discloses a crystalline fluorocarbon polymer, and U.S. patent nos. 5015693 and 4855013 to Duchesne and Johnson, disclose a processing aid that uses a poly (oxyalkylene) polymer as a synergist in combination with the fluorocarbon polymer. It can be seen that many of the patents relate to replacing 50-80% of fluoropolymer with synergist such as polyethylene glycol or polycaprolactone, and although the addition of polyethylene glycol or polyester synergist can greatly reduce the content of fluoropolymer, so as to reduce the cost, the performance of the processing aid is also reduced at the same time of the addition.
Therefore, it is important to develop a processing aid for polyolefin-based polymers at low cost without deteriorating the properties.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a processing aid for thermoplastic polymers, wherein a polyalkylacrylate is added into the processing aid to serve as a synergist, the addition of the synergist can reduce the content of fluorine-containing polymers, and the use effect of the processing aid is maintained or even improved; in addition, the price of the polyalkyl acrylate is only 20-30% of that of the fluorine-containing polymer, so the addition of the polyalkyl acrylate can greatly reduce the cost of the processing aid.
In order to achieve the above object, a first aspect of the present invention provides a processing aid for thermoplastic polymers, which adopts the following technical scheme:
a processing aid for thermoplastic polymers, the processing aid comprising, in weight percent: 10-70 wt% (e.g., 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%) of a polyalkylacrylate, the balance being a fluoropolymer; wherein the weight average molecular weight of the polyalkylacrylate is greater than 15 ten thousand.
Among the above processing aids for thermoplastic polymers, as a preferred embodiment, the weight average molecular weight of the polyalkenyl polyacrylate is 30 to 200 ten thousand (e.g., 50 ten thousand, 80 ten thousand, 100 ten thousand, 150 ten thousand, 180 ten thousand); more preferably, the weight average molecular weight of the polyalkenyl polyacrylate is from 50 to 150 ten thousand (e.g., 60 ten thousand, 80 ten thousand, 110 ten thousand, 120 ten thousand, 130 ten thousand).
The fluorine-containing polymer and the polyalkylacrylate in the processing aid are mutually fused to form elastic particles, preferably, the particle size of the fluorine-containing polymer emulsion in the raw material of the processing aid is 200-500 nm (such as 250nm, 300nm, 350nm, 400nm and 450nm), and the particle size of the polyalkylacrylate emulsion is 100-300 nm (such as 120nm, 150nm, 180nm, 200nm and 250 nm).
In the above processing aid for thermoplastic polymer, as a preferred embodiment, the processing aid further comprises 0 to 70 wt% (e.g., 10 wt%, 20 wt%, 30 wt%, 45 wt%, 60 wt%) of polyethylene glycol or polyester and the fluoropolymer is at least 10 wt%; preferably, the polyethylene glycol or polyester has a weight average molecular weight of 1000-; preferably, the weight ratio of the polyalkylacrylate to fluoropolymer in the processing aid is from 1:1 to 2:1 (e.g., 1:1.2, 1:1.5, 1:1.7, 1: 1.9); preferably, the polyester is selected from one or more of polyethylene glycol succinate, polybutylene succinate-1, 4-butylene succinate, polyethylene adipate, polybutylene adipate-1, 4-butylene succinate, polylactic acid, polycaprolactone and block copolymers thereof.
The polyethylene glycol or polyester is used as a surfactant and has the following characteristics: the extrusion temperature is liquid or molten; (ii) lower melt viscosity than the non-fluorinated melt processable polymer, the fluoropolymer and the polyalkylacrylate elastomer; (iii) is free wetting but not fusing to the fluoropolymer and polyalkylacrylate elastomer. The polyethylene glycol or polyester added in the invention can be mutually fused with the fluorine-containing polymer and the polyalkyl acrylate to form elastomer particles without forming a coating state.
Among the above processing aids for thermoplastic polymers, as a preferred embodiment, the polyalkylacrylate is an elastomer at normal temperature (25 ℃); preferably, the glass transition temperature of the polyalkylacrylate is less than 10 ℃; more preferably, the glass transition temperature of the polyalkenyl acrylate is below 0 ℃.
In the present invention, the low glass transition temperature reflects the uniformity of formation of the polyalkylacrylate by copolymerization of different monomers, and the polymer with uniformly copolymerized monomers has low crystallinity, and is less likely to affect the light transmittance and gloss of the thermoplastic polymer (polyolefin) being processed as a processing aid.
In the above processing aid for thermoplastic polymer, as a preferred embodiment, the preparation method of the processing aid comprises: firstly, obtaining a polyalkylacrylate emulsion by an emulsion polymerization method, then adding the polyalkylacrylate emulsion into a fluorine-containing polymer emulsion, uniformly stirring, and finally co-coagulating to obtain a processing aid; preferably, when the processing aid further comprises polyethylene glycol or polyester, the preparation method of the processing aid comprises the following steps: firstly, obtaining a polyalkylacrylate emulsion by an emulsion polymerization method, then adding the polyalkylacrylate emulsion into a fluorine-containing polymer emulsion, uniformly stirring to obtain a mixed emulsion, adding polyester, and performing coagglomeration to obtain a processing aid, or directly performing coagglomeration on the mixed emulsion and then mixing polyethylene glycol to obtain the processing aid; preferably, the average particle size of the polyalkylacrylate emulsion is 100-300 nm (such as 120nm, 150nm, 180nm, 200nm, 250nm) and the solid content is 15-45% (such as 18%, 20%, 25%, 30%, 40%); preferably, the fluoropolymer emulsion has a latex particle size of 200-500 nm (e.g., 250nm, 300nm, 350nm, 400nm, 450nm) and a solids content of 15-45% (e.g., 18%, 20%, 25%, 30%, 40%).
In the processing aid for thermoplastic polymers, as a preferred embodiment, the polyalkylacrylate is obtained by homopolymerizing or copolymerizing one or more monomers of acrylate monomers, carboxylic acid group-containing ethylenically unsaturated copolymerizable monomers, and saturated fatty acid esterified alkenyl alcohol monomers; preferably, the polyalkyl acrylate is prepared by copolymerizing a plurality of monomers of acrylate monomers, carboxylic acid group-containing ethylenically unsaturated copolymerizable monomers and saturated fatty acid esterified alkenyl alcohol monomers.
The polyalkyl acrylate in the present invention is preferably obtained by copolymerizing 39.5 to 80 wt% (e.g., 40 wt%, 45 wt%, 50 wt%, 60 wt%, 70 wt%) of ethyl acrylate, 19.5 to 60 wt% (e.g., 20 wt%, 30 wt%, 40 wt%, 50 wt%, 55 wt%) of butyl acrylate, 0.5 to 15 wt% (e.g., 1 wt%, 2 wt%, 5 wt%, 8 wt%, 12 wt%) of acrylic acid; more preferably, the polyalkylacrylate is obtained by copolymerizing 43 to 75 wt% (such as 48 wt%, 52 wt%, 56 wt%, 65 wt%, 72 wt%) ethyl acrylate, 23 to 55 wt% (such as 25 wt%, 32 wt%, 35 wt%, 42 wt%, 48 wt%) butyl acrylate, 2 to 12 wt% (such as 4 wt%, 7 wt%, 8 wt%, 9 wt%, 11 wt%) acrylic acid; preferably, the polyalkylacrylate is obtained by copolymerizing 50 to 70 wt% (such as 52 wt%, 55 wt%, 60 wt%, 62 wt%, 65 wt%) of butyl acrylate, 15 to 40 wt% (such as 18 wt%, 22 wt%, 28 wt%, 35 wt%, 38 wt%) of 2-methoxyethyl acrylate, 2 to 10 wt% (such as 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%) of ethyl acrylate, and 2 to 12 wt% (such as 4 wt%, 6 wt%, 8 wt%, 10 wt%, 11 wt%) of acrylic acid; preferably, the polyalkyl acrylate is copolymerized from 50-85 wt% (e.g., 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%) butyl acrylate and 15-50 wt% (e.g., 18 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%) vinyl acetate.
In the above processing aid for thermoplastic polymers, as a preferred embodiment, the acrylic ester monomer has a general structural formula: CH (CH)2＝CR1-COOR2(ii) a Wherein R is1Is a hydrogen atom or an alkyl group of 1 to 10 (e.g. 2, 4, 6, 8) carbon atoms, R2Alkyl, cycloalkyl, aryl or oxyalkyl of 1 to 10 (such as 2, 4, 6, 8) carbon atoms; preferably, R1Is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R2Is alkyl, cycloalkyl, aryl or oxyalkyl of 1 to 4 carbon atoms; preferably, the acrylic ester monomer is selected from one or more of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, methoxy methyl acrylate, ethoxy methyl acrylate, 2-methoxy ethyl acrylate and 2-ethoxy ethyl acrylate; preferably, the acrylate monomer is selected from one or more of methyl methacrylate, ethyl acrylate, butyl acrylate and 2-methoxyethyl acrylate.
Among the above-mentioned processing aids for thermoplastic polymers,as a preferred embodiment, the carboxylic acid group-containing ethylenically unsaturated copolymerizable monomer has the general structural formula: r3CH＝CR4COOH, wherein, R3Is a hydrogen atom or an alkyl, cycloalkyl, aryl, fatty acid or fatty acid ester of 1 to 10 (e.g. 2, 4, 6, 8) carbon atoms, R4Alkyl, cycloalkyl, aryl, fatty acid or fatty acid ester which is a hydrogen atom or 1 to 10 (such as 2, 4, 6, 8) carbon atoms; preferably, R3Is a hydrogen atom or an alkyl, fatty acid or fatty acid ester of 1 to 6 carbon atoms, R4Is a hydrogen atom or an alkyl, fatty acid or fatty acid ester of 1 to 4 carbon atoms; preferably, the ethylenically unsaturated copolymerizable monomer containing a carboxylic acid group is selected from one or more of acrylic acid, methacrylic acid, α -ethacrylic acid, crotonic acid, cinnamic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl fumarate, monoethyl fumarate, mono-n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono-n-butyl maleate, monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexene fumarate, monocyclopentyl maleate, monocyclohexyl maleate, monocyclohexene maleate, monomethyl itaconate, monoethyl itaconate, mono-n-butyl itaconate and monocyclohexyl itaconate; preferably, the ethylenically unsaturated copolymerizable monomer containing carboxylic acid group is selected from one or more of acrylic acid, methacrylic acid, monoethyl fumarate, mono-n-butyl fumarate, monoethyl maleate and mono-n-butyl maleate.
In the above processing aid for thermoplastic polymers, as a preferred embodiment, the saturated fatty acid esterified alkenyl alcohol monomer has a general structural formula: CH (CH)2＝CHOCOR5(ii) a Wherein R is5An alkyl, cycloalkyl or aryl group which is a hydrogen atom or 1 to 10 (such as 2, 4, 6, 8) carbon atoms; preferably, R5Is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms; preferably, the monomer of said esterified alkenyl alcohol of saturated fatty acid is selected from vinyl formate, vinyl acetate, vinyl propionateOne or more of vinyl n-butyrate, vinyl isobutyrate and vinyl benzoate; preferably, the monomer of said fatty acid esterified alkenyl alcohol is selected from vinyl acetate.
Among the above processing aids for thermoplastic polymers, as a preferred embodiment, the fluoropolymer is an elastomeric fluoropolymer and a thermoplastic fluoropolymer; preferably, the fluoropolymer is a homopolymer of an unsaturated fluoromonomer or a copolymer of a plurality of unsaturated fluoromonomers; more preferably, the fluorine-containing monomer is selected from one or more of monochlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, fluoroalkyl ethylene and fluoroalkyl fluorovinyl ether; preferably, the fluorine-containing polymer is one or more selected from hexafluoropropylene-tetrafluoroethylene copolymer (F46), vinylidene fluoride-hexafluoropropylene copolymer (F26), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer and ethylene-tetrafluoroethylene copolymer (F40).
The method used in the present invention for identifying a polyalkylacrylate elastomer may be:
measuring the molecular weight of the polyacrylate by using a coagulation permeation chromatography (GPC), wherein the weight average molecular weight is required to be more than 150000;
measuring the glass transition temperature (Tg) of the polyalkylacrylate by using Differential Scanning Calorimetry (DSC), wherein the glass transition temperature is required to be lower than 10 ℃;
thirdly, the structure of the poly (alkylene acrylate) is qualitatively analyzed by using an infrared spectroscopy (IR), as shown in figure 1, the characteristic infrared absorption peaks of the functional group ester group are 1720-1739cm-1And 1150-1165cm-1Nearby.
And fourthly, the characteristic fragments of the polyalkylacrylate, such as butyl acrylate, ethyl acrylate and the like, can be obviously seen when the thermal cracking gas mass spectrometer (PY-GCMS) is used for measurement.
In a second aspect, the present invention provides a melt processable composition comprising a thermoplastic polymer and a processing aid for the thermoplastic polymer as described above, the processing aid for the thermoplastic polymer being present in an amount of from 0.005 to 50% (e.g. 0.01%, 0.1%, 1%, 5%, 25%, 45%) by weight of the melt processable composition.
In the above melt processable composition, as a preferred embodiment, the thermoplastic polymer is a polyolefin, a polyvinyl resin, a polystyrene, a polyurethane, and a polyketone; preferably, the thermoplastic polymer is a polyolefin, the monomer of which has the general structural formula CH2Where R is a hydrogen atom or an alkyl group of 1 to 10 (such as 2, 4, 6, 8) carbon atoms; more preferably, R is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; more preferably, the thermoplastic polymer is one or more of High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), metallocene linear low density polyethylene (mLLDPE), polypropylene (PP), ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol ester copolymer and ethylene-acrylic acid (salt) copolymer.
The thermoplastic polymers of the present invention may be used in the form of powders, pellets, granules or any other processable extruded form. It is also contemplated that the thermoplastic polymer may be used in combination with conventional additives including light stabilizers, antioxidants, antiblocking agents, slip agents, lubricants, fillers, flame retardants, blowing agents, nucleating agents, clarifying agents, colorants, coupling agents, compatibilizers, antistatic agents, antifogging agents, heat stabilizers, plasticizers, metal scavengers, acid/base scavengers, antimicrobial agents, or other combinations.
The melt processable compositions of the present invention can be prepared by any of a number of methods, for example, the thermoplastic polymer and the processing aid can be mixed by any mixing device commonly employed in the plastics industry, such as with a mixing roll mill, internal mixer, or mixing extruder in which the processing aid can be uniformly dispersed within the thermoplastic polymer. The processing aids and thermoplastic polymers can be used, for example, in the form of powders, pellets or granules. The mixing operation is most commonly carried out at a temperature above 120 ℃, the components are pre-mixed in the form of solid particles, and then the dry mixture is fed into a twin-screw extruder to uniformly disperse the processing aid components; the solid particles can be fed at different feeding ports of a double-screw extruder according to required proportion respectively, and the processing aid can be uniformly dispersed.
The resulting mixture can be pelletized or otherwise comminuted to the desired particle size and particle size respectively and fed to an extruder, typically a single screw extruder. The melt processing temperature is typically 160 ℃ to 280 ℃, and the optimum processing temperature is selected based on the melting point, melting point viscosity, and thermal stability of the mixture. The die design of the extruder can vary depending on the desired extrudate shape and is not particularly limited.
Mixing the processing aid into the thermoplastic polymer, forming master batch by a double-screw extruder, diluting and mixing the master batch and the thermoplastic polymer according to the concentration of the processing aid required to be added, and finally feeding the mixture into the extruder and processing the mixture into a required shape by a die head. The thermoplastic polymers to be processed may contain conventional additives, such as fillers, pigments, slip agents and antioxidants.
Compared with the prior art, the invention has the following advantages:
the processing aid for the thermoplastic polymer is added with the polyalkylacrylate as a synergist, so that the content of the fluorine-containing polymer can be reduced, and the use effect of the processing aid is maintained or even improved; in addition, the price of the polyalkyl acrylate is only 20-30% of that of the fluorine-containing polymer, so that the cost of the processing aid can be greatly reduced.
Drawings
FIG. 1 is an IR spectrum of a polyalkylacrylate obtained in example 1 of the present invention;
FIG. 2 is an IR spectrum of a melt processable composition from example 1 of the present invention;
FIG. 3 is a mass spectrum of a polyalkyl acrylate obtained in example 1 of the present invention;
FIG. 4 is a comparative graph of melt fracture elimination for processing aids of examples 1,4, 1, 3, 5 of the present invention;
FIG. 5 is a comparative graph of melt fracture elimination for processing aids of example 2 of the present invention and comparative example 2;
FIG. 6 is a comparative graph of melt fracture elimination for processing aids of example 3 of the present invention and comparative example 4.
Detailed Description
The processing aids for thermoplastic polymers and the melt processable compositions of the present invention are further explained below with reference to the figures and examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by one skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the invention as defined by the appended claims.
The% not particularly specified in the present invention are weight percentages. The starting materials used in the examples below are all commercially available.
The main components of the processing aids prepared in the examples of the present invention and the comparative examples are shown in table 1 below.
Table 1 shows the main components of the processing aids obtained in examples 1 to 4 and comparative examples 1 to 5
| Fluorine-containing polymer | Polyalkylacrylate elastomer | Polyethylene glycol | Polyester | |
| Example 1 | 33.4％ | 66.6％ | 0 | 0 |
| Example 2 | 25％ | 25％ | 0 | 50％ |
| Example 3 | 10％ | 20％ | 70％ | 0 |
| Example 4 | 30％ | 60％ | 0 | 10％ |
| Comparative example 1 | 100％ | 0 | 0 | 0 |
| Comparative example 2 | 50％ | 0 | 0 | 50％ |
| Comparative example 3 | 30％ | 60％ | 0 | 10％ |
| Comparative example 4 | 30％ | 0 | 70％ | 0 |
| Comparative example 5 | 33.4％ | 66.6％ | 0 | 0 |
Example 1 preparation and use of a processing aid for PPA-1 thermoplastic polymers
(1) Adding 56.5 parts by weight of ethyl acrylate, 33.5 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid and 0.01 part by weight of n-dodecyl mercaptan as a molecular weight regulator into a container with stirring and mixing functions, and uniformly stirring to obtain a monomer mixture;
then, 400 parts by weight of water, 0.6 part by weight of sodium stearate and 0.04 part by weight of potassium persulfate were charged into a reactor equipped with a heating and stirring device, stirred and heated to 65 ℃, and then the monomer mixture obtained above was uniformly and continuously charged into the reactor over 2 to 3 hours, and after keeping the temperature for 0.5 hour, cooled to 30 ℃ to obtain a polyacrylate emulsion. The latex particle diameter is 127nm, the solid content is 20%, the weight average molecular weight of the polyacrylate is 134 ten thousand measured by GPC method, the infrared spectrogram is shown in figure 1, and the characteristic absorption peak in the infrared spectrogram is 1731cm-1And 1159cm-1Nearby. When the obtained polyacrylate was measured by a thermal cracking gas mass spectrometer (PY-GCMS), it was found that characteristic peaks of butyl acrylate and ethyl acrylate were contained in characteristic fragments of polyacrylate as shown in fig. 3(a) and 3 (b).
(2) Adding 167 parts (weight) of vinylidene fluoride-hexafluoropropylene copolymer concentrated dispersion (FKM emulsion L636 emulsion, 30% solid content Solvay Solexis S.P.A, latex particle diameter 385nm) into the polyacrylate emulsion to obtain an emulsion mixture;
then, 300 parts by weight of water, 30 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 15 parts by weight of calcium chloride as a coagulant were added to a coagulant equipped with a heating and stirring device to prepare a coagulated solution. The emulsion mixture obtained above was added uniformly and continuously over 1 hour while heating to 60 ℃, 15 parts by weight of activated calcium phosphate was added, and after cooling, filtration was carried out to obtain water-containing elastic particles. The aqueous elastic particles were repeatedly washed with water 4 times and centrifuged, and dried at 100 ℃ to a constant weight to obtain a processing aid for thermoplastic polymers having a fluoropolymer content of about 33.4% and a polyalkylacrylate elastomer content of 66.6%, which was designated as PPA-1.
Preparation of melt processable compositions: uniformly mixing 3 parts by weight of PPA-1 and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and bracing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain a processing aid master batch with the PPA-1 content of 3%, and marking as MB-1; the infrared spectrum is shown in figure 2.
Example 2 preparation and use of processing aid for PPA-2 thermoplastic Polymer
(1) In a vessel with stirring and mixing, 56.5 parts by weight of ethyl acrylate, 33.5 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid and 0.07 part by weight of n-dodecyl mercaptan as a molecular weight modifier were added and stirred uniformly to obtain a monomer mixture.
Then, 400 parts by weight of water, 0.6 part by weight of sodium stearate and 0.05 part by weight of potassium persulfate were charged into a reactor equipped with a heating and stirring device, stirred and heated to 65 ℃, and then the monomer mixture obtained above was uniformly and continuously charged into the reactor over 2 to 3 hours, and after keeping the temperature for 0.5 hour, cooled to 30 ℃ to obtain a polyacrylate emulsion. The latex was sampled and examined to have a particle diameter of 102nm and a solid content of 20%, and the polyacrylate had a weight average molecular weight of 56 ten thousand as measured by GPC.
(2) 333 parts by weight of a concentrated dispersion of a vinylidene fluoride-hexafluoropropylene copolymer (FKM emulsion L636 emulsion, 30% solids Solvay Solexis S.P.A., latex particle size 385nm) was added to the above polyacrylate emulsion to obtain an emulsion mixture;
then, 300 parts by weight of water, 30 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 15 parts by weight of calcium chloride as a coagulant were added to a coagulant equipped with a heating and stirring device to prepare a coagulated solution. Heating to 60 deg.C, adding the obtained emulsion mixture uniformly and continuously within 1 hr, adding 200 parts (by weight) of polycaprolactone with molecular weight of 3200 uniformly and continuously within 0.5 hr, cooling to below 40 deg.C, and filtering to obtain water-containing elastic particles. Repeatedly washing the water-containing elastic particles for 4 times, centrifuging and filtering, and drying at 50 ℃ to constant weight to obtain the processing aid for the thermoplastic polymer with the fluoropolymer content of about 25%, the polyalkylacrylate elastomer content of 25% and the polycaprolactone content of 50%, which is marked as PPA-2.
Preparation of melt processable compositions: uniformly mixing 3 parts by weight of PPA-2 and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-2 content of 3%, and marking as MB-2.
Example 3 preparation and use of processing aid for PPA-3 thermoplastic Polymer
30 parts by weight of PPA-1 obtained in example 1 was taken and added to a dispersion machine, and 70 parts by weight of polyethylene glycol having a molecular weight of 10000 was added thereto and mixed uniformly to obtain a processing aid for thermoplastic polymers having a fluoropolymer content of 10%, a polyalkylacrylate elastomer content of 20%, and a polyethylene glycol content of 70%, which was designated as PPA-3.
Preparation of melt processable compositions: uniformly mixing 3 parts by weight of PPA-3 and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-3 content of 3%, and marking as MB-3.
Example 4 preparation and use of processing aid for PPA-4 thermoplastic Polymer
(1) In a vessel with stirring and mixing, 56.5 parts by weight of ethyl acrylate, 33.5 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid and 0.01 part by weight of n-dodecyl mercaptan as a molecular weight modifier were added and stirred uniformly to obtain a monomer mixture.
Then, 400 parts by weight of water, 0.6 part by weight of sodium stearate and 0.04 part by weight of potassium persulfate were charged into a reactor equipped with a heating and stirring device, stirred and heated to 65 ℃, and then the monomer mixture obtained above was uniformly and continuously charged into the reactor over 2 to 3 hours, and after keeping the temperature for 0.5 hour, cooled to 30 ℃ to obtain a polyacrylate emulsion. The latex was sampled and examined to have a particle diameter of 127nm and a solid content of 20%, and the polyacrylate had a weight average molecular weight of 134 ten thousand as measured by GPC.
(2) Adding 167 parts (weight) of vinylidene fluoride-hexafluoropropylene copolymer concentrated dispersion (FKM emulsion L636 emulsion, 30% solid content Solvay Solexis S.P.A, latex particle diameter 385nm) into the polyacrylate emulsion to obtain an emulsion mixture;
then, 300 parts by weight of water, 30 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 15 parts by weight of calcium chloride as a coagulant were added to a coagulant equipped with a heating and stirring device to prepare a coagulated solution. The emulsion mixture obtained above was added uniformly and continuously over 1 hour while heating to 60 ℃, followed by adding 16 parts by weight of polybutylene adipate with a molecular weight of 2000 uniformly and continuously over 0.5 hour, cooling to 40 ℃ or less, and filtering to obtain water-containing elastic particles. Repeatedly washing the water-containing elastic particles for 4 times, centrifuging and filtering, and drying at 50 ℃ to constant weight to obtain the processing aid for the thermoplastic polymer with the fluorine-containing polymer content of about 30%, the polyalkylacrylate elastomer content of 60% and the polycaprolactone content of 10%, which is marked as PPA-4.
Preparation of melt processable compositions: uniformly mixing 3 parts by weight of PPA-4 and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-4 content of 3%, and marking as MB-4.
Comparative example 1 preparation and use of PPA-X Process aid
300 parts by weight of water, 30 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 15 parts by weight of calcium chloride as a coagulant were charged into a reactor with heating and stirring to prepare a coagulated solution. Heating to 60 ℃, uniformly and continuously adding 333 parts by weight of concentrated dispersion liquid of vinylidene fluoride-hexafluoropropylene copolymer (FKM emulsion L636 emulsion, 30% solid content Solvay Solexis S.P.A, latex particle diameter 385nm) in 1 hour, after finishing adding, adding 15 parts by weight of active calcium phosphate, cooling and filtering to obtain the water-containing elastic particles. The aqueous elastomeric particles were repeatedly washed 4 times with water and centrifuged, and dried at 100 ℃ to constant weight to give a processing aid having a fluoropolymer content of about 100%, designated PPA-X.
Uniformly mixing 3 parts by weight of PPA-X and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-X content of 3%, and marking as MB-X.
Comparative example 2 preparation and use of PPA-Y Process aid
150 parts by weight of water, 15 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 5 parts by weight of calcium chloride as a coagulant were added to a heated and stirred tank to prepare a coagulated solution. Heating to 60 deg.C, adding 167 weight parts of concentrated dispersion of vinylidene fluoride-hexafluoropropylene copolymer (FKM emulsion L636 emulsion, 30% solid content Solvay Solexis S.P.A, latex particle diameter 385nm) uniformly and continuously in 1 hr, adding 50 weight parts of polycaprolactone with molecular weight of 3200 in 0.5 hr after dropping, cooling to below 40 deg.C, and filtering to obtain water-containing elastic particles. Repeatedly washing the water-containing elastic particles for 4 times, centrifuging and filtering, and drying at 50 ℃ to constant weight to obtain the processing aid with the fluoropolymer content of 50% and the polycaprolactone content of 50%, which is marked as PPA-Y.
Uniformly mixing 3 parts by weight of PPA-Y and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-Y content of 3%, and marking as MB-Y.
Comparative example 3 preparation and use of PPA-W Process aid
Into a reactor equipped with a heating and stirring device, 400 parts by weight of deionized water, 32 parts by weight of sodium chloride, 0.32 part by weight of nonylphenol polyoxyethylene ether were charged, the pH was adjusted to 5 with an olefinic hydrochloric acid, 0.04 part by weight of potassium persulfate was added with stirring, and 56.5 parts by weight of ethyl acrylate, 33.5 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid, and 0.01 part by weight of n-dodecyl mercaptan as a molecular weight modifier were added. Controlling the temperature to be lower than 50 ℃, dropwise adding 167 parts by weight of vinylidene fluoride-hexafluoropropylene copolymer concentrated dispersion (FKM emulsion L636 emulsion with the solid content of 30% Solvay Solexis S.P.A and the latex particle diameter of 385nm) within 1 hour, after dropwise adding, adding 24 parts by weight of active calcium phosphate, slowly introducing nitrogen to expel oxygen, raising the temperature to 50 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, adding 16 parts by weight of polybutylene adipate with the molecular weight of 2000, raising the temperature to 70 ℃, preserving heat for 4 hours, finally raising the temperature to 90 ℃, preserving heat for 3 hours, after the particles are settled out, removing the nitrogen, introducing water vapor for 30 minutes to cure the particles and driving off unreacted substances. And (3) introducing cooling water while stirring, discharging after the temperature of the reactor is lower than 35 ℃, repeatedly washing the particles for 4 times, centrifugally filtering, and drying at 50 ℃ to constant weight to obtain the processing aid with the fluoropolymer content of about 30%, the polyalkylacrylate elastomer content of 60% and the polybutylene adipate content of 10%, which is marked as PPA-W.
Uniformly mixing 3 parts by weight of PPA-W and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-W content of 3%, and marking as MB-W.
Comparative example 4 preparation and use of PPA-Z Process aid
Adding 30 parts by weight of PPA-X obtained in the comparative example 1 into a dispersion machine, adding 70 parts by weight of polyethylene glycol with the molecular weight of 10000, and uniformly mixing to obtain the processing aid with the fluoropolymer content of 30% and the polyethylene glycol content of 70%, wherein the processing aid is marked as PPA-Z.
Uniformly mixing 3 parts by weight of PPA-Z and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-Z content of 3%, and marking as MB-Z.
Comparative example 5 preparation and use of PPA-V Process aid
(1) Adding 56.5 parts by weight of ethyl acrylate, 33.5 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid and 0.22 part by weight of n-dodecyl mercaptan as a molecular weight regulator into a container with stirring and mixing, and uniformly stirring to obtain a monomer mixture;
then, 400 parts by weight of water, 0.6 part by weight of sodium stearate and 0.20 part by weight of potassium persulfate were charged into a reactor equipped with a heating and stirring device, stirred and heated to 65 ℃, and then the monomer mixture obtained above was uniformly and continuously charged into the reactor over 2 to 3 hours, and after keeping the temperature for 0.5 hour, cooled to 30 ℃ to obtain a polyacrylate emulsion. The latex had a particle size of 112nm as measured by sampling and a solid content of 20%, and the weight average molecular weight of the polyacrylate was 7 ten thousand as measured by GPC.
(2) Adding 167 parts (weight) of vinylidene fluoride-hexafluoropropylene copolymer concentrated dispersion (FKM emulsion L636 emulsion, 30% solid content Solvay Solexis S.P.A, latex particle diameter 385nm) into the polyacrylate emulsion to obtain an emulsion mixture;
then, 300 parts by weight of water, 30 parts by weight of an aqueous polyvinyl alcohol solution (having a solid content of 10%) and 15 parts by weight of calcium chloride as a coagulant were added to a coagulant equipped with a heating and stirring device to prepare a coagulated solution. The emulsion mixture obtained above was added uniformly and continuously over 1 hour while heating to 60 ℃, 15 parts by weight of activated calcium phosphate was added, and after cooling, filtration was carried out to obtain water-containing elastic particles. The aqueous elastic particles were repeatedly washed with water 4 times and centrifuged, and dried at 100 ℃ to a constant weight to give a processing aid for thermoplastic polymers having a fluoropolymer content of about 33.4% and a polyalkylacrylate elastomer content of 66.6%, designated PPA-V.
Uniformly mixing 3 parts by weight of PPA-V and 97 parts by weight of thermoplastic polyolefin resin LLDPE, continuously feeding into a double-screw extruder, extruding and drawing at 190 ℃, cooling and solidifying in a water bath, granulating and drying to obtain the processing aid master batch with the PPA-V content of 3%, and marking as MB-V.
Evaluation test
Extrusion processability evaluation was performed on a film blowing machine, where the length to diameter ratio of the extruder was 24/1, with four independently temperature controlled temperature zones, with a die head diameter of 40mm and a gap of 1.25 mm. In the evaluation test, the temperature zones of 1-4 sections of the extruder were set to 150 ℃, 180 ℃, 200 ℃ and 200 ℃, respectively, and the die temperature was maintained at 200 ℃. LLDPE having a melt index of 0.9(g/10min) was used as the base resin for evaluation, and the critical shear rate on a film blowing machine under these conditions was 120s-1At greater than or equal to this shear rate, the resulting film is 100% melt fractured. When a comparative evaluation test is carried out, the screw rotating speed of the film blowing machine is set to be kept at 55rpm, the extrusion capacity is 22kg/h, and the time is 300s-1The shear rate of (c). A small section of the film was cut every 5min, spread out and the length of melt fracture was measured with a ruler in the direction perpendicular to the extrusion, to convert the melt fracture ratio of the film.
Before each evaluation, the polyolefin washer stock with 20% silicate content was continuously extruded for 60min, and then the blank polyolefin resin LLDPE (MI 0.9) was continuously extruded for 30min, ensuring that the melt pressure, screw torque were in equilibrium processing conditions and the entire film was in a fully collapsed condition.
The processing aid master batch MB with the PPA content of 3% and the base resin particles are compounded according to a certain proportion by a weighing mode, and mixtures to be tested with different PPA concentrations can be obtained. To compare the performance of each PPA sample in parallel, the same masterbatch carrier resin (LLDPE with melt index 2), the evaluation test body resin (LLDPE with melt index 0.9), the process parameters and the same PPA concentration of 400ppm were used in the evaluation test.
The performance results of the processing aids prepared in examples 1-4 and comparative examples 1-5 are shown in Table 2; the comparative graph of the melt fracture elimination of the processing aid in the inventive examples 1,4, 1, 3 and 5 is shown in FIG. 4; the comparative graph of melt fracture elimination for the processing aids of inventive example 2 and comparative example 2 is shown in FIG. 5; the comparative graph of melt fracture elimination for the processing aids of inventive example 3 and comparative example 4 is shown in FIG. 6.
Table 2 shows extrusion processability of the processing aids obtained in examples 1 to 4 and comparative examples 1 to 5
From the above data, it can be seen that processing aids made using gum elastomers comprised of polyalkylacrylate and fluoropolymer in a weight ratio of 1:1 to 2:1 perform better than processing aids made using the same gum content but only fluoropolymer as the gum elastomer. Therefore, the invention provides the polyalkylacrylate elastomer as a synergist, and the effect of the processing aid can be maintained or even improved under the condition of adding the synergist and reducing the fluorine-containing polymer.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. A processing aid for thermoplastic polymers, characterized in that it comprises, in weight percent: 10-70 wt% of polyalkylacrylate, and the balance of fluoropolymer; wherein the weight average molecular weight of the polyalkylacrylate is greater than 15 ten thousand.
2. The processing aid for thermoplastic polymers according to claim 1, wherein the weight average molecular weight of the polyalkenyl polyacrylate is 30 to 200 ten thousand; more preferably, the weight average molecular weight of the polyalkenyl polyacrylate is from 50 to 150 ten thousand.
3. A processing aid for thermoplastic polymers according to claim 1 or 2, characterized in that it further comprises 0-70 wt% of polyethylene glycol or polyester and at least 10 wt% of fluoropolymer; preferably, the polyethylene glycol or polyester has a weight average molecular weight of 1000-;
preferably, the weight ratio of the polyalkylacrylate to fluoropolymer in the processing aid is from 1:1 to 2: 1.
4. The processing aid for thermoplastic polymers according to any one of claims 1 to 3, wherein the polyalkylacrylate is an elastomer at normal temperature; preferably, the glass transition temperature of the polyalkylacrylate is less than 10 ℃; more preferably, the glass transition temperature of the polyalkenyl acrylate is below 0 ℃.
5. The processing aid for thermoplastic polymers according to any one of claims 1 to 4, characterized in that it is prepared by a process comprising: firstly, obtaining a polyalkylacrylate emulsion by an emulsion polymerization method, then adding the polyalkylacrylate emulsion into a fluorine-containing polymer emulsion, uniformly stirring, and finally co-coagulating to obtain a processing aid;
preferably, when the processing aid further comprises polyethylene glycol or polyester, the preparation method of the processing aid comprises the following steps: firstly, obtaining a polyalkylacrylate emulsion by an emulsion polymerization method, then adding the polyalkylacrylate emulsion into a fluorine-containing polymer emulsion, uniformly stirring to obtain a mixed emulsion, adding polyester, and performing coagglomeration to obtain a processing aid, or directly performing coagglomeration on the mixed emulsion and then mixing polyethylene glycol to obtain the processing aid;
preferably, the average particle size of the polyalkylacrylate emulsion is 100-300 nm, and the solid content is 15-45%;
preferably, the particle size of the fluorine-containing polymer emulsion is 200-500 nm, and the solid content is 15-45%.
6. The processing aid according to any one of claims 1 to 5, wherein the polyalkenyl acrylate is obtained by homopolymerization or copolymerization of one or more monomers selected from acrylate monomers, ethylenically unsaturated copolymerizable monomers containing carboxylic acid groups, and ethylenically unsaturated fatty acid esterified alkenyl monomers; preferably, the polyalkyl acrylate is copolymerized from a plurality of acrylate monomers, ethylenically unsaturated copolymerizable monomers containing carboxylic acid groups, and saturated fatty acid esterified alkenyl alcohol monomers.
7. The processing aid according to any one of claims 1 to 6, wherein the acrylate-based monomer has a general structural formula: CH (CH)2＝CR1-COOR2(ii) a Wherein R is1Is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, R2Is alkyl, cycloalkyl, aryl or oxyalkyl of 1 to 10 carbon atoms;
preferably, the carboxylic acid group-containing ethylenically unsaturated copolymerizable monomer has the general structural formula: r3CH＝CR4COOH, wherein, R3Is a hydrogen atom or an alkyl, cycloalkyl, aryl, fatty acid or fatty acid ester of 1 to 10 carbon atoms, R4Is a hydrogen atom or an alkyl, cycloalkyl, aryl, fatty acid or fatty acid ester of 1 to 10 carbon atoms;
preferably, the structural general formula of the saturated fatty acid esterified enol monomer is as follows: CH (CH)2＝CHOCOR5(ii) a Wherein R is5Is a hydrogen atom or an alkyl, cycloalkyl or aryl group of 1 to 10 carbon atoms.
8. The processing aid for thermoplastic polymers according to any one of claims 1 to 7, wherein the fluoropolymer is an elastomeric fluoropolymer and a thermoplastic fluoropolymer; preferably, the fluoropolymer is a homopolymer of an unsaturated fluoromonomer or a copolymer of a plurality of unsaturated fluoromonomers.
9. A melt processable composition comprising a thermoplastic polymer and a processing aid for the thermoplastic polymer according to any one of claims 1 to 8, wherein the weight of the processing aid for the thermoplastic polymer is from 0.005 to 50% of the weight of the melt processable composition.
10. A melt processable composition according to claim 9 wherein the thermoplastic polymer is a polyolefin, a polyvinyl resin, a polystyrene, a polyurethane, or a polyketone;
preferably, the thermoplastic polymer is a polyolefin, the monomers of which have the general structural formula CH2(ii) CHR, wherein R is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; more preferably, R is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; more preferably, the thermoplastic polymer is one or more of high density polyethylene, low density polyethylene, linear low density polyethylene, metallocene linear low density polyethylene, polypropylene, ethylene vinyl alcohol copolymer, ethylene vinyl alcohol ester copolymer, and ethylene acrylic acid copolymer.
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| PCT/CN2023/070430 WO2023138375A1 (en) | 2022-01-18 | 2023-01-04 | Processing aid for thermoplastic polymer, and melt-processable composition comprising processing aid |
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| WO2023138375A1 (en) * | 2022-01-18 | 2023-07-27 | 广州熵能创新材料股份有限公司 | Processing aid for thermoplastic polymer, and melt-processable composition comprising processing aid |
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| CN114381078B (en) * | 2022-01-18 | 2022-10-11 | 广州熵能创新材料股份有限公司 | Processing aid for thermoplastic polymer and melt-processable composition containing same |
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