CN105315441A - Application of fatty acid modified hyperbranched polyester to plastic processing - Google Patents
Application of fatty acid modified hyperbranched polyester to plastic processing Download PDFInfo
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- CN105315441A CN105315441A CN201510872292.2A CN201510872292A CN105315441A CN 105315441 A CN105315441 A CN 105315441A CN 201510872292 A CN201510872292 A CN 201510872292A CN 105315441 A CN105315441 A CN 105315441A
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- branched polyester
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- 229920003023 plastic Polymers 0.000 title claims abstract description 73
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- 229930195729 fatty acid Natural products 0.000 title claims abstract description 71
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- 238000012545 processing Methods 0.000 title claims abstract description 15
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- 239000000203 mixture Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 229940059574 pentaerithrityl Drugs 0.000 claims description 15
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001261 hydroxy acids Chemical class 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229940033355 lauric acid Drugs 0.000 claims description 3
- 229960004232 linoleic acid Drugs 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 18
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses application of fatty acid modified hyperbranched polyester to plastic processing, belonging to the technical field of plastic processing aids. The application of fatty acid modified hyperbranched polyester comprises the steps of adding 0.5-3% of fatty acid modified hyperbranched polyester into plastics, uniformly mixing, extruding for granulating, and drying to obtain a modified plastic product. Plastics including polypropylene and the like are modified through mixing the plastics including polypropylene and the like and hyperbranched polyester at a high speed, and then, granulating by extruding through a double-screw extruder; the hyperbranched polyester is added into plastic matrixes, so that the processing temperature of the plastics can be remarkably lowered, the apparent property of the plastics is improved, and relatively high melting flowability is realized through relatively low additive amount; the decomposition temperature of the fatty acid modified hyperbranched polyester is relatively high and can be up to 290 DEG C; and the melt index of the modified plastics is remarkably increased, and meanwhile the dispersing performance of a filling system is improved.
Description
Technical field
The invention belongs to the technical field of plastic processing additives, refer to the application of a kind of fatty acid modified hyper-branched polyester in plastic working especially.
Background technology
Hyperbranched polymer (Hyperbranchedpolymer, HBP) is the emerging macromolecular material of a class, has 3-D solid structure, molecular structure is more regular, relative molecular mass distribution is very narrow feature.HBP has the spheroidal compact form of class, molecular entanglement is few, thus viscosity with relative molecular mass increase change less, and due in molecule with many end functional groups, the character such as viscosity, solvability, thermostability, second-order transition temperature and relative molecular mass distribution are had a significant impact.Hyperbranched polymer has the structure (tree structure) of class tree-shaped, because it is similar to branch-shape polymer, physicals also possesses the advantage similar to branch-shape polymer; But the cost of its synthesis and purifying is but low relative to branch-shape polymer.Hyperbranched polymer has good solubility, lower melt viscosity, and relative to linear polymer surface functional group very high density; Because above-mentioned feature makes HBP have good magnetism in blended applications, its special construction makes it in the physical properties improving blend, have very large potentiality, as processibility, crystallization behavior, mechanical property etc.This product can have unique application performance in the plastics such as PP, PE, PC, PS, PPC, ABS, PET, PBT, PLA poly(lactic acid) or PA.
Hyperbranched polymer adds effective melt viscosity that significantly can reduce the plastics such as polypropylene in the plastics substrates such as polypropylene to, namely reduces processing temperature, improves the apparent property of plastics; In addition, lower addition can realize the melt fluidity strengthened so equally, can be used for complicated or thin articles injection-moulded; Improve the yield strength of plastics, tensile modulus, Notched Izod Impact Strength and flexural strength, and then improve mechanical property and the processing characteristics of plastics; Overcome melt viscosity in plastic processes larger, mobility is poor, it is shaping that lesser temps is difficult to processing plasticizing, the not full and macroscopic irregularity such as current mark, crazing of large-scale injection molding, the injection moulding of thin-walled injection molding part, can also overcome the performance deficiency that blown film outward appearance is rough, film bubble is unstable, became uneven is even.
Existing hyperbranched polymer is used as the auxiliary agent of plastic working and also there is a lot of defect, and, the large and impact of its addition and govern the cost of modifying plastics, energy consumption and performance.
Summary of the invention
The invention provides the application of a kind of fatty acid modified hyper-branched polyester in plastic working, solve hyper-branched polyester decomposition temperature in prior art low, suitability for industrialized production can not be realized and addition is large and affect the problem of the cost of modifying plastics, energy consumption and performance in the plastic.
The application of a kind of fatty acid modified hyper-branched polyester of the present invention in plastic working, it mainly realizes by the following technical programs so in addition: join in plastics by fatty acid modified hyper-branched polyester according to the addition that mass percent is 0.5-3%, mix, extruding pelletization, drying, obtains the plastic prod of modification.
As the preferred embodiment of one, comprise the following steps: a) that fatty acid modified hyper-branched polyester is dry, cooling, pulverizes, and screening is for subsequent use; B) plastics are dry, cooling, for subsequent use; C) by the fatty acid modified hyper-branched polyester of step a) gained and the plastics of step b) gained, mixing, obtains mixture, for subsequent use; D) twin screw extruder is warmed up to 120-230 DEG C, after preheating 1-2h, by step b) gained mixture, drops into twin screw extruder, extruding pelletization; E) particle step d) produced, at 80 DEG C, dry 4-8h, obtains the plastic prod of modification.
As the preferred embodiment of one, the preparation method of described fatty acid modified hyper-branched polyester is: 1) in polyol compound, add poly-hydroxy carboxylic compound, and add catalyzer, poly-hydroxy carboxylic compound is 3-16:1 with the ratio of the molar mass of polyol compound, and the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass; 2) under protection of inert gas, 120-180 DEG C is warming up to, reaction 2-8h; Then, at reduced pressure conditions, reaction is proceeded; When the acid number of reaction is less than 30mgKOH/g, reaction terminates, and obtains first-generation hyper-branched polyester, and end functional group number is 6-32; 3) in first-generation hyper-branched polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 6-32 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain s-generation hyper-branched polyester, end functional group number is 12-64; 4) in s-generation hyper-branched polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 12-64 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain third generation hyper-branched polyester, end functional group number is 24-128; 5) by that analogy, obtain N-Generation hyper-branched polyester, N is natural number, and functional group number is 3 × 2
n-16 × 2
nindividual; 6) N-Generation hyper-branched polyester is got, add lipid acid and catalyzer, the molar mass of lipid acid is the 10-100% of N-Generation hyper-branched polyester terminal functionality total mole number, the quality of catalyzer is the 0.2%-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain the hyper-branched polyester that N-Generation is fatty acid modified.
As the preferred embodiment of one, in described step 6), lipid acid is the lipid acid containing 3-30 carbon atom; Described step 2) in, the temperature of reaction is 160 DEG C, and reduced pressure is Absolute truth reciprocal of duty cycle is-0.1MPa to-0.07MPa; The modification ratio of described fatty acid modified hyper-branched polyester is 10-100%.
As the preferred embodiment of one, described polyol compound is the derivative of polyvalent alcohol or polyvalent alcohol, and described polyvalent alcohol is one or more in tetramethylolmethane, TriMethylolPropane(TMP), glycerol, dipentaerythritol; Described poly-hydroxy carboxylic compound is one or more in polycarboxylic acid, multi-hydroxy carboxy acid, poly-hydroxy acid anhydrides; Described lipid acid is one or more in sad, n-nonanoic acid, certain herbaceous plants with big flowers acid, oleic acid, linolic acid, soybean oil, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid; Described catalyzer is one or more in tosic acid, butyl (tetra) titanate, dibutyl tin laurate, stannous octoate.
As the preferred embodiment of one, described fatty acid modified hyper-branched polyester is terminal hydroxy group aliphatics hyper-branched polyester, and its modification ratio is 40%, and decomposition temperature is 290 DEG C; Described lipid acid is the lipid acid containing 5-20 carbon atom.Here modification ratio be n
1/ n
2× 100%, n
1for the mole number of the lipid acid functional group of modified hyper-branched polyester, n
2the mole number of the end functional group (i.e. hydroxyl) of hyper-branched polyester before modified.
As the preferred embodiment of one, described fatty acid modified hyper-branched polyester is one or more in the hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the first-generation, the s-generation, the third generation, forth generation, the 5th fat subsitutes acid modification; The addition of described fatty acid modified hyper-branched polyester is 1-3%.
As the preferred embodiment of one, in described step d), there is 5-10 temperature control district in twin screw extruder, and the processing temperature in each temperature control district is 205-215 DEG C; Described twin screw extruder is parallel dual-screw extruding machine, and its engine speed is 150-400r/min, and rate of feeding is 15-30Hz.
As the preferred embodiment of one, in described step a), fatty acid modified hyper-branched polyester carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h, adopts 30 object screen clothes to sieve; In described step b), plastics carry out drying in the air dry oven of 80 DEG C, and time of drying is 2-3h; In described step e), the particle produced carries out drying in convection oven.
As the preferred embodiment of one, in described step c), plastics and fatty acid modified hyper-branched polyester mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 500-1500r/min; Described plastics are one or more in PP, PE, PC, PS, PPC, ABS, PET, PBT, PLA poly(lactic acid) or PA.The preferred PP of the present invention has carried out systematic difference research as application system.
Beneficial effect of the present invention: the present invention is by the plastics such as polypropylene and hyper-branched polyester melt blending and completed the modification of the plastics such as polypropylene by twin screw extruder, hyper-branched polyester adds effective melt viscosity that significantly can reduce the plastics such as polypropylene in the plastics substrates such as polypropylene to, namely reduce processing temperature, improve the apparent property of the plastics such as polypropylene; In addition, lower addition can realize the melt fluidity strengthened so equally, can be used for complicated or thin articles injection-moulded; Improve the yield strength of the plastics such as polypropylene, tensile modulus, Notched Izod Impact Strength and flexural strength, and then the mechanical property and the processing characteristics that improve the plastics such as polypropylene; Overcome melt viscosity in the plastic processes such as polypropylene larger, mobility is poor, it is shaping that lesser temps is difficult to processing plasticizing, the not full and macroscopic irregularity such as current mark, crazing of large-scale injection molding, the injection moulding of thin-walled injection molding part, also overcomes the product defects that blown film outward appearance is rough, film bubble is unstable, became uneven is even.The melting means of the plastics such as modified polypropylene is significantly improved, and meanwhile, improves the dispersing property of infill system; Reduce the tooling cost of the plastics such as polypropylene, addition is few compared with similar products, and cost is low.This new hyperbranched polyester decomposition temperature is higher, reaches 290 DEG C, and may be used for suitability for industrialized production, cost is low, industrialization promotion is easy.
Embodiment
Be clearly and completely described technical scheme of the present invention below in conjunction with specific embodiments of the invention, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
embodiment one
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add dimethylol propionic acid 482Kg and tetramethylolmethane 122Kg, add 3Kg stannous octoate catalyst, under nitrogen protection, be heated to 160 DEG C, reaction 6h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be first-generation superbrnaching end-hydroxy polyester, be denoted as HBPE-10, terminal hydroxy group number is 8.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 360KgHBPE-10, and add 492Kg palmitic acid and 4.26Kg butyl (tetra) titanate, under nitrogen protection, be heated to 160 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when the acid number of reaction system is lower than 30mgKOH/g, reaction terminates; Cooling, obtain Solid Modified after hyper-branched polyester, be the hyper-branched polyester that the first-generation is fatty acid modified, be designated as HBPE-11.
In the present invention, in the building-up reactions of first-generation superbrnaching end-hydroxy polyester, dimethylol propionic acid is 4:1 with the ratio of the molar mass of tetramethylolmethane, and certainly, dimethylol propionic acid and the ratio of the molar mass of tetramethylolmethane also can be other any number in 3:1-16:1.The addition of the sub-tin of octoate catalyst can also be other any number in 0.2-8%.Temperature of reaction also can be other arbitrary temp of 120-180 DEG C, and the reaction times also can be other random time in 2-8h, and the end functional group number of gained first-generation superbrnaching end-hydroxy polyester can also be other any number in 6-32.
embodiment two
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 225KgHBPE-10 and 402Kg dimethylol propionic acid, add 3.135Kg tosic acid, under helium protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be s-generation superbrnaching end-hydroxy polyester, be denoted as HBPE-20, its end functional group number is 16.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 360KgHBPE-20, and add 386.14Kg palmitic acid and 3.74Kg butyl (tetra) titanate, under helium protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction system is lower than 30mgKOH/g, reaction terminates; Cooling, obtain Solid Modified after hyper-branched polyester, be the hyper-branched polyester that the s-generation is fatty acid modified, be designated as HBPE-22.
In the present invention, in the building-up reactions of s-generation superbrnaching end-hydroxy polyester, dimethylol propionic acid is 12:1 with the ratio of the molar mass of tetramethylolmethane, and certainly, dimethylol propionic acid and the ratio of the molar mass of tetramethylolmethane also can be other any number in 6:1-32:1.
In the present invention, the molar mass that palmitic acid adds can also be the Arbitrary Digit between the 10-100% of the N-Generation superbrnaching end-hydroxy polyester terminal functionality total mole number corresponding with it; The quality that catalyzer adds can also be the Arbitrary Digit between the 0.2-8% of the poly-hydroxy such as polyol compound and the dimethylol propionic acid carboxylic compound total masses such as tetramethylolmethane.
embodiment three
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 260KgHBPE-20 and 364Kg dimethylol propionic acid, add 3.12Kg tosic acid, under nitrogen protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be third generation superbrnaching end-hydroxy polyester, be denoted as HBPE-30, terminal hydroxy group number is 32.
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 300KgHBPE-30, and add 290.72Kg palmitic acid and 1.8Kg butyl (tetra) titanate, under nitrogen protection, be heated to 160 DEG C, reaction 4h; Under vacuumized conditions, continue reaction, when the acid number of reaction system is lower than 30mgKOH/g, reaction terminates; Cooling, obtain Solid Modified after hyper-branched polyester, be the hyper-branched polyester that the third generation is fatty acid modified, be designated as HBPE-33.
In the present invention, in the building-up reactions of third generation superbrnaching end-hydroxy polyester, dimethylol propionic acid is 28:1 with the ratio of the molar mass of tetramethylolmethane, and certainly, dimethylol propionic acid and the ratio of the molar mass of tetramethylolmethane also can be other any number in 12:1-64:1.
In the present invention, lipid acid is the lipid acid containing 3-30 carbon atom, and its modification ratio is 10-100%; Preferably, lipid acid is the lipid acid containing 5-20 carbon atom, and its modification ratio is 40%; Certainly, above-mentioned tetramethylolmethane also can be one or more in the derivative of other polyvalent alcohols such as TriMethylolPropane(TMP), glycerol, dipentaerythritol or polyvalent alcohol.Above-mentioned 2,2-dimethylol propionic acids also can be the poly-hydroxy carboxylic compounds such as other multi-hydroxy carboxy acids such as dimethylolpropionic acid, polycarboxylic acid, acid anhydrides, poly-hydroxy acid anhydrides.Above-mentioned catalyzer also can be one or more in tosic acid, dibutyl tin laurate, stannous octoate.Above-mentioned palmitic acid also can be one or more in sad, n-nonanoic acid, certain herbaceous plants with big flowers acid, oleic acid, linolic acid, soybean oil, laurostearic acid, TETRADECONIC ACID, stearic acid.
embodiment four
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 290KgHBPE-30 and 367Kg dimethylol propionic acid, add 3.28Kg tosic acid, under protection of inert gas, be heated to 160 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when the acid number of reaction is less than 30mgKOH/g, reaction terminates, and cooling, obtain water white transparency solid, be forth generation superbrnaching end-hydroxy polyester, be denoted as HBPE-40, terminal hydroxy group number is 64.
In 1 ton of reactor that mechanical stirring, thermometer and spherical reflux exchanger are housed, add 288KgHBPE-40, and add 266.16Kg palmitic acid and 2.77Kg butyl (tetra) titanate, under protection of inert gas, be heated to 150 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when the acid number of reaction system is lower than 30mgKOH/g, reaction terminates; Cooling, obtain Solid Modified after hyper-branched polyester, be the hyper-branched polyester that forth generation is fatty acid modified, be designated as HBPE-44.
In the present invention, in the building-up reactions of forth generation superbrnaching end-hydroxy polyester, dimethylol propionic acid is 60:1 with the ratio of the molar mass of tetramethylolmethane, and certainly, dimethylol propionic acid and the ratio of the molar mass of tetramethylolmethane also can be other any number in 24:1-128:1.
embodiment five
In 1 ton of reactor that mechanical stirring, thermometer and reflux exchanger are housed, add 290KgHBPE-40 and 350Kg dimethylol propionic acid, add 3.2Kg tosic acid, under nitrogen gas protection, be heated to 140 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when reaction acid number be less than 30mgKOH/g, reaction terminate, cooling, obtain water white transparency solid, be the 5th generation superbrnaching end-hydroxy polyester, be denoted as HBPE-50, terminal hydroxy group number is 128.
In 1 ton of reactor that mechanical stirring, thermometer and spherical reflux exchanger are housed, add 240KgHBPE-50, and add 216.9Kg palmitic acid and 2.28Kg butyl (tetra) titanate, under nitrogen gas protection, be heated to 140 DEG C, reaction 3h; Under vacuumized conditions, continue reaction, when the acid number of reaction system is lower than 30mgKOH/g, reaction terminates; Cooling, obtain Solid Modified after hyper-branched polyester, be the 5th fat subsitutes acid modification hyper-branched polyester, be designated as HBPE-55.
In the present invention, the 5th generation superbrnaching end-hydroxy polyester building-up reactions in, dimethylol propionic acid is 124:1 with the ratio of the molar mass of tetramethylolmethane, and certainly, dimethylol propionic acid and the ratio of the molar mass of tetramethylolmethane also can be other any number in 48:1-256:1.
embodiment six
Hyper-branched polyester (HBPE-22) drying that s-generation embodiment two prepared is fatty acid modified, cooling, pulverizes, and screening is for subsequent use; Polypropylene is dry, cooling, for subsequent use; Get above-mentioned fatty acid modified hyper-branched polyester and above-mentioned polypropylene, mixing, obtain mixture, the addition of now fatty acid modified hyper-branched polyester is 0.5%, for subsequent use; Twin screw extruder is warmed up to 120 DEG C, after preheating 1h, by said mixture, drops into twin screw extruder, extruding pelletization; Twin screw extruder is parallel dual-screw extruding machine, and its engine speed is 150r/min, and rate of feeding is 30Hz; By the particle produced, at 80 DEG C, dry 6h, obtains the polypropylene product of modification.
The addition of hyper-branched polyester fatty acid modified in the present invention adopts mass percent to represent, namely addition adopts the ratio of the quality of fatty acid modified hyper-branched polyester and polyacrylic quality to represent; Such as in the present embodiment, the addition of fatty acid modified hyper-branched polyester is 0.5%, namely in quality is to add the fatty acid modified hyper-branched polyester that quality is 0.5 part in the polypropylene of 100 parts.
embodiment seven
The hyper-branched polyester (HBPE-44) that forth generation embodiment four prepared is fatty acid modified, at the dry 5h of vacuum drying oven under room temperature, is put in dry seal cavity cool to room temperature, this material is white or light yellow solid, pulverize, and use 30 object screen clothes to sieve, for subsequent use; Polypropylene is placed in the convection oven of 80 DEG C, dry 2-3h, is put in dry seal cavity cool to room temperature, this material is white translucent or White-opalescent powder or particle; Above-mentioned polypropylene and fatty acid modified hyper-branched polyester are put in the high-speed mixer of 500r/min and mix 3min, wherein, the addition of fatty acid modified hyper-branched polyester is 1%; Then, import in hermetically drying hopper, for subsequent use; By twin screw extruder 8 warm area heating all to 205 DEG C, after preheating 1-2h, blanking extruding pelletization; Wherein, twin screw extruder is parallel dual-screw extruding machine, and its engine speed is 400r/min, and rate of feeding is 30Hz; Then, the particle produced is put in dry 4-8h in 80 DEG C of convection oven temperature, obtains the polypropylene product of modification.
embodiment eight
The hyper-branched polyester (HBPE-55) of the 5th fat subsitutes acid modification embodiment five prepared, at the dry 7h of vacuum drying oven under room temperature, pulverizes, screening, for subsequent use; Polypropylene is placed in the convection oven of 80 DEG C, dry 2.5h, is put in dry seal cavity cool to room temperature; Polypropylene and above-mentioned new hyperbranched polyester (HBPE-11) are put in high-speed mixer and mix 6min, wherein, the addition of fatty acid modified hyper-branched polyester is 2%; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 10 warm areas are all heated to 210 DEG C, after preheating 1.5h, blanking extruding pelletization; Then, the particle produced is put in dry 5h in 80 DEG C of convection oven temperature, obtains the polypropylene product of modification.
embodiment nine
Hyper-branched polyester (HBPE-44) composition mixture that the forth generation of the hyper-branched polyester (HBPE-33) that the third generation prepared of the fatty acid modified hyper-branched polyester (HBPE-11) of the first-generation, embodiment three prepared by Example one is fatty acid modified and embodiment four preparation is fatty acid modified, and at the dry 6h of vacuum drying oven under room temperature, pulverize, screening, for subsequent use; Polypropylene is placed in the convection oven of 80 DEG C, dry 2h, is put in dry seal cavity cool to room temperature; The new hyperbranched polyester mixture got after polypropylene and above-mentioned screening is put in the high-speed mixer of 1500r/min and mixes 4.5min, and wherein, the addition of new hyperbranched polyester mixture is 3%; Then, import in hermetically drying hopper, for subsequent use; Twin screw extruder 5 warm areas are all heated to 230 DEG C, after preheating 1h, blanking extruding pelletization; Wherein, twin screw extruder is parallel dual-screw extruding machine, and its engine speed is 300r/min, and rate of feeding is 25Hz; Then, the particle produced is put in the convection oven temperature of 80 DEG C, dry 6h, obtains the polypropylene product of modification.
Certainly, this fatty acid modified hyper-branched polyester also can be in HBPE-11, HBPE-22, HBPE-33, HBPE-44, HBPE-55 other any one or multiple mixture; Polypropylene of the present invention also can be one or more in PE, PC, PS, PPC, ABS, PET, PBT, PLA poly(lactic acid) or PA.
By four of the embodiment of the present invention six to embodiment nine kinds of modified polypropenes and neat polypropylene pellets, carry out Mechanics Performance Testing experiment respectively, its tensile strength and elongation at break is measured according to the method for GB/T1040-2006, its complete intensity and modulus in flexure is measured according to the method for GB/T9341-2008, its shock strength is measured according to the method for GB/T1843-2008, measure its melting index (abbreviation melting means) when 230 DEG C/2.16kg according to the method for GB/T3682-2000, experimental results is as shown in table 1.
The physicals of the hyper-branched polyester that table 1PP/ is fatty acid modified
| Sequence number | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (MPa) | Shock strength (KJ/m 2） | Melting means (g/10min) |
| Testing method | GB/T 1040-2006 | GB/T 1040-2006 | GB/T 9341-2008 | GB/T 9341-2008 | GB/T 1843-2008 | GB/T 3682-2000 |
| Pure PP | 27.74 | 565.68 | 26.33 | 991.81 | 2.493 | 15.91 |
| 1 | 28.72 | 568.95 | 26.67 | 1005.34 | 2.498 | 21.41 |
| 2 | 28.76 | 558.29 | 27.03 | 1015.86 | 2.504 | 22.45 |
| 3 | 29.00 | 589.45 | 26.81 | 1004.99 | 2.678 | 25.87 |
| 4 | 28.21 | 578.56 | 26.39 | 998.02 | 2.712 | 26.98 |
Adopt numeral 1 to 4 correspondingly to represent enforcement six to embodiment nine respectively in table 1, as can be seen from Table 1, through the polypropylene that fatty acid modified hyper-branched polyester is modified, its tensile strength slightly promotes; Meanwhile, its elongation at break remains unchanged substantially; Its flexural strength slightly promotes or remains unchanged; Modulus in flexure slightly promotes; Modified polyacrylic shock strength is slightly promoted; Its melting index comparatively virgin pp significantly improves, and obtains significantly or double lifting; Namely modified polypropylene substantially increases the flowing property adding man-hour; And in the process of polypropylene modification, the addition of fatty acid modified hyper-branched polyester is few, easy to process, and cost is low.
Beneficial effect of the present invention: the present invention is by the plastics such as polypropylene and hyper-branched polyester melt blending and completed the modification of the plastics such as polypropylene by twin screw extruder, hyper-branched polyester adds effective melt viscosity that significantly can reduce the plastics such as polypropylene in the plastics substrates such as polypropylene to, namely reduce processing temperature, improve the apparent property of the plastics such as polypropylene; In addition, lower addition can realize the melt fluidity strengthened so equally, can be used for complicated or thin articles injection-moulded; Improve the yield strength of the plastics such as polypropylene, tensile modulus, Notched Izod Impact Strength and flexural strength, and then the mechanical property and the processing characteristics that improve the plastics such as polypropylene; Overcome melt viscosity in the plastic processes such as polypropylene larger, mobility is poor, it is shaping that lesser temps is difficult to processing plasticizing, the not full and macroscopic irregularity such as current mark, crazing of large-scale injection molding, the injection moulding of thin-walled injection molding part, also overcomes the performance deficiency that blown film outward appearance is rough, film bubble is unstable, became uneven is even.The melting means of the plastics such as modified polypropylene is significantly improved, and meanwhile, improves the dispersing property of infill system; Reduce the tooling cost of the plastics such as polypropylene, addition is few compared with similar products, and cost is low.This new hyperbranched polyester decomposition temperature is higher, reaches 290 DEG C, and may be used for suitability for industrialized production, cost is low, industrialization promotion is easy.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the application of fatty acid modified hyper-branched polyester in plastic working, is characterized in that:
Fatty acid modified hyper-branched polyester is joined in plastics according to the addition that mass percent is 0.5-3%, mixes, extruding pelletization, dry, obtain the plastic prod of modification.
2. the application of fatty acid modified hyper-branched polyester according to claim 1 in plastic working, is characterized in that, comprise the following steps:
A) described fatty acid modified hyper-branched polyester is dry, cooling, pulverizes, and screening is for subsequent use;
B) plastics are dry, cooling, for subsequent use;
C) by the fatty acid modified hyper-branched polyester of step a) gained and the plastics of step b) gained, mixing, obtains mixture, for subsequent use;
D) twin screw extruder is warmed up to 120-230 DEG C, after preheating 1-2h, by step b) gained mixture, drops into twin screw extruder, extruding pelletization;
E) particle step d) produced, at 80 DEG C, dry 4-8h, obtains the plastic prod of modification.
3. the application of fatty acid modified hyper-branched polyester according to claim 1 and 2 in plastic working, is characterized in that, the preparation method of described fatty acid modified hyper-branched polyester is:
1) in polyol compound, add poly-hydroxy carboxylic compound, and adding catalyzer, poly-hydroxy carboxylic compound is 3-16:1 with the ratio of the molar mass of polyol compound, and the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass;
2) under protection of inert gas, 120-180 DEG C is warming up to, reaction 2-8h; Then, at reduced pressure conditions, reaction is proceeded; When the acid number of reaction is less than 30mgKOH/g, reaction terminates, and obtains first-generation hyper-branched polyester, and end functional group number is 6-32;
3) in first-generation hyper-branched polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 6-32 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain s-generation hyper-branched polyester, end functional group number is 12-64;
4) in s-generation hyper-branched polyester, continue to add poly-hydroxy carboxylic compound and catalyzer, the addition of poly-hydroxy carboxylic compound is 12-64 times of polyol compound molar mass, the addition of catalyzer is the 0.2-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain third generation hyper-branched polyester, end functional group number is 24-128;
5) by that analogy, obtain N-Generation hyper-branched polyester, N is natural number, and functional group number is 3 × 2
n-16 × 2
nindividual;
6) N-Generation hyper-branched polyester is got, add lipid acid and catalyzer, the molar mass of lipid acid is the 10-100% of N-Generation hyper-branched polyester terminal functionality total mole number, the quality of catalyzer is the 0.2%-8% of polyol compound and poly-hydroxy carboxylic compound total mass, repeat above-mentioned reaction, obtain the hyper-branched polyester that N-Generation is fatty acid modified.
4. the application of fatty acid modified hyper-branched polyester according to claim 3 in plastic working, is characterized in that:
In described step 6), lipid acid is the lipid acid containing 3-30 carbon atom;
Described step 2) in, the temperature of reaction is 160 DEG C, and reduced pressure is Absolute truth reciprocal of duty cycle is-0.1MPa to-0.07MPa;
The modification ratio of described fatty acid modified hyper-branched polyester is 10-100%.
5. the application of fatty acid modified hyper-branched polyester according to claim 3 in plastic working, is characterized in that:
Described polyol compound is the derivative of polyvalent alcohol or polyvalent alcohol, and described polyvalent alcohol is one or more in tetramethylolmethane, TriMethylolPropane(TMP), glycerol, dipentaerythritol;
Described poly-hydroxy carboxylic compound is one or more in polycarboxylic acid, multi-hydroxy carboxy acid, poly-hydroxy acid anhydrides;
Described lipid acid is one or more in sad, n-nonanoic acid, certain herbaceous plants with big flowers acid, oleic acid, linolic acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid;
Described catalyzer is one or more in tosic acid, butyl (tetra) titanate, dibutyl tin laurate, stannous octoate.
6. the application of fatty acid modified hyper-branched polyester according to claim 4 in plastic working, is characterized in that:
Described fatty acid modified hyper-branched polyester is terminal hydroxy group aliphatics hyper-branched polyester, and its modification ratio is 40%, and decomposition temperature is 290 DEG C;
Described lipid acid is the lipid acid containing 5-20 carbon atom.
7. the application of fatty acid modified hyper-branched polyester according to claim 3 in plastic working, is characterized in that:
Described fatty acid modified hyper-branched polyester is one or more in the hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the fatty acid modified hyper-branched polyester of the first-generation, the s-generation, the third generation, forth generation, the 5th fat subsitutes acid modification;
The addition of described fatty acid modified hyper-branched polyester is 1-3%.
8. the application of fatty acid modified hyper-branched polyester according to claim 5 in plastic working, is characterized in that:
In described step d), there is 5-10 temperature control district in twin screw extruder, and the processing temperature in each temperature control district is 205-215 DEG C;
Described twin screw extruder is parallel dual-screw extruding machine, and its engine speed is 150-400r/min, and rate of feeding is 15-30Hz.
9. the application of fatty acid modified hyper-branched polyester according to claim 8 in plastic working, is characterized in that:
In described step a), fatty acid modified hyper-branched polyester carries out drying under room temperature in vacuum drying oven, and time of drying is 5-7h, adopts 30 object screen clothes to sieve;
In described step b), plastics carry out drying in the air dry oven of 80 DEG C, and time of drying is 2-3h;
In described step e), the particle produced carries out drying in convection oven.
10. the application of fatty acid modified hyper-branched polyester according to claim 9 in plastic working, is characterized in that:
In described step c), plastics and fatty acid modified hyper-branched polyester mix in high-speed mixer, and mixing time is 3-6min, and mixing velocity is 700-1500r/min;
Described plastics are one or more in PP, PE, PC, PS, PPC, ABS, PET, PBT, PLA poly(lactic acid) or PA.
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