CN103626982B - A kind of method improving the melt strength of polyester resin - Google Patents
A kind of method improving the melt strength of polyester resin Download PDFInfo
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Abstract
A kind of method improving the melt strength of polyester resin, mainly comprise the following steps: A, using the monomer containing active function groups as the first monomer, using another or various of monomer as comonomer, preparation is containing the multipolymer intermediate of active function groups, and the active function groups in this multipolymer intermediate has clear and definite position and quantity; B, by solution reaction or melt blending reaction, utilize, containing the multipolymer intermediate of active function groups, the molecule of polyester resin is carried out coupling, make polyester macromolecule produce branched structure, thus improve the melt strength of polyester resin.Adopt method of the present invention, greatly can improve the melt strength of polyester resin, the branched polyester material prepared by the inventive method can be applied to foaming, melt-spinning or field of thin film fabrication.
Description
Technical field
The present invention relates to chemical engineering, particularly relate to a kind of method improving the melt strength of polyester resin.
Background technology
Polyester refers to the polymkeric substance general name by polyvalent alcohol and polyprotonic acid polycondensation, main finger polyethylene terephthalate (PET), also comprising linear thermoplastic's resins such as polybutylene terephthalate (PBT) and polyarylester traditionally, is a class excellent performance, broad-spectrum engineering plastics.And poly(lactic acid) (PLA) is through intermolecular dehydration by lactic acid, come by esterification Step Condensation another kind of can the polyester material of complete biodegradable, its final degraded product is carbonic acid gas and water, intermediate product lactic acid is also normal carbohydrate metabolism product in body, harmless and in vivo without accumulation, having good bio-compatibility and excellent processing characteristics, is one of the most valued material in field of medical materials.
Although the polyester material that PET and PLA is representative is widely used in some fields, but due to them or have good mechanical property, resistance to elevated temperatures, or there is unrivaled biodegradable performance, people wish them to be applied to foaming field more, substitute in the market a large amount of urethane (PU) porous plastics, polystyrene (PS) porous plastics and polyethylene (PE) porous plastics used.Although these three kinds of porous plastics of PU, PS, PE bring facility to our production and life in early days, but along with the exhaustion of petroleum resources and people more and more pay attention to environment, the shortcoming of these three kinds of porous plastics looms large day by day: polyurethane foam not only exists harmful isocyanic ester residue in the base, and be thermosetting material due to it, so waste cannot be recycled; And polystyrene usually can use Hydrochlorofluorocarbons (HCFC) or butane in foaming process, have disadvantageous effect to environment, and product degraded difficulty easily forms " white pollution ", environmental protection organization of United Nations has determined to stop using PS foamed products; Polyethylene foams rigidity is lower, and maximum operation (service) temperature is only 80 DEG C, can not meet the service requirements in some needs high strength or high temperature resistant field.Therefore, researcher is striving to find their substitute always, at present, except polypropylene (PP), PET and PLA is that the polyester foam of representative is considered to the most promising, is expected to thermoplastic resin that current froth product is upgraded.
Although PP foam material is owing to having good thermostability (maximum operation (service) temperature reaches 130 DEG C), the dimensional stability of goods and higher toughness, tensile strength and shock strength under high temperature and by large quantity research, but compared with PP foam material, PET is that the polyester foam materials of representative has unique premium properties: the dimensional stability that (1) is desirable, good barrier is had, excellent wear resistance and surperficial retardation capability to oxygen, carbonic acid gas and steam; (2) better heat stability, its maximum operating temperature about 200 DEG C, far above the working temperature of PP, PS, PU, polyvinyl chloride (PVC) foam; (3) mechanical property is far above PS, PU foam and glass foam, can use as structural support material, based on the excellent properties of above advantage and PET itself, PET foam material has wide market in food product pack, microwave container, sports equipment, microelectronic product, automobile and space industry etc.And the foamed products of PLA has good flexibility and feel, and the most important thing is that its biological degradability is that petroleum-based plastics is unrivaled, therefore PLA foam has a good application prospect in fields such as packaging, medical treatment and consumer goods.
Although the foamed products of polyester resin has so many advantage, but from PS, LDPE two kinds of resins without processing modified just directly can carry out physics or chemical foaming different, polyester resin is linear polymeric, be elevated to after more than fusing point in temperature, matrix viscosity can sharply diminish, and due to the unstable (being easily hydrolyzed) of ester group, easily cause molecular rupture, melt viscosity is reduced further, so gas is difficult to be encased by melt in foaming process, easily there is the generation of the phenomenons such as abscess merges, cave in.Therefore, many investigators are devoted to the foam performance improving vibrin, wherein improving the most effective means of melt strength is make polymkeric substance produce branched structure, the generation of branched structure significantly can change the rheological behaviour of melt, improve melt strength, improve its foaming, fibroblast and film forming properties, thus cause more research and larger concern.In addition, in the melt-spinning process of PET, in order to improve the production efficiency of PET, reduce production cost further, one of feasible way is exactly improve spinning production rate.And for normal linear polyester material, the slippage between molecular chain easily occurs its melt in drawing process, once the excessive necking penomena that will produce of draw speed, thin neck ruptures thereupon, thus occurs the fracture of wire phenomenon of fiber.And improve one of main path of terylene melt-spinning speed in PET matrix, introduce long-chain branch (LCB) structure exactly, the existence of LCB structure makes melt filament when thin neck occurs, its viscosity is made sharply to increase, therefore thin neck can not rupture, but extend to whole fiber, namely there is " strain hardening " phenomenon.
PLA fiber has the similar physical property of same PET, not only has high crystalline, also has the similar transparency.Owing to having high crystalline and high orientation, PLA fiber has high heat resistance and high strength, and without the need to special equipment and operating procedure, the complete processing of application routine just can carry out spinning.But PLA fiber is different from the PET of aromatic ester, its melt-spinning be shaped comparatively PET difficulty, be mainly manifested in the contradiction between the thermo-sensitivity of PLA and melt high viscosity.The PLA relative molecular weight that such as can be used for spinning technique reaches about 100,000, but its melt viscosity near fusing point is far above the viscosity of PET melt, PLA is made to have good mobility and spinning property when spinning technique, certain spinning temperature must be reached, but PLA material at high temperature, very easily there is thermal destruction when especially standing the relatively-high temperature of long period, therefore cause the temperature range of PLA melt molding extremely narrow.Branched structure is introduced in PLA, its molecular weight can be improved on the one hand, even if make its generation DeR also can not worsen the spinning properties of PLA matrix, branched structure can improve the melt viscosity of PLA resin when high temperature on the other hand, therefore greatly can widen the melt molding temperature of PLA.
The branched structure of long chain branch PET can be introduced in the course of the polymerization process, such as patent of invention CN102492124A provide a kind of with aromatic dicarboxylic acid or derivatives thereof, dibasic alcohol and polyfunctional group chainextender for raw material, the method for long-chain branched polyester that obtains of direct esterification melt polycondensation reaction in the presence of a catalyst.Patent of invention CN102492123A provide a kind of with the polyfunctional group chainextender of aromatic dicarboxylic acid or derivatives thereof, dibasic alcohol and polyprotonic acid, polynary ester for raw material, the long-chain branched polyester that obtains of direct esterification melt polycondensation reaction in the presence of a catalyst.But for this multi-functional polyreaction, easily generate a large amount of gels in the course of the polymerization process, gel content can reach more than 40% sometimes, greatly have impact on processing characteristics and the mechanical property of polyester matrix.Although can by the content regulating the content of polyfunctional monomer to reduce gel, but reduce the density that polyfunctional monomer will certainly affect side chain, the melt strength of vibrin can not be increased substantially, more can not need according to practical application the degree of branching controlling vibrin.
The introducing of side chain also can be realized by the method adding branching agent in extrusion, as extrude add add man-hour epoxy compounds, isocyanic ester, acid anhydrides,
the chainextenders such as azoles quinoline, can make the viscosity of polyester resin obtain rising to a certain extent.Patent CN1325420 provides a kind of method preparing PET foam article, comprise: under the mixture containing following component being heated to be not less than the temperature of melting point polyester, to prepare, there is the swelling vibrin in 50 grams/10 minutes or lower melt flow rate (MFR) and 10-200%; Then under the help of whipping agent, this vibrin is carried out heat foamable, wherein this mixture comprises (a) 100 line style saturated polyester of weight part; The coupling agent mixture of (b) 0.1-10 weight part, its forming containing the compound of two epoxy group(ing) and the compound containing two or more epoxy group(ing) of 100-0 % by weight in the molecule by 0-100 % by weight; (c) 0.01-5 weight part is as the carboxylic metallic salt of coupling reaction catalyst.Patent CN102807743A relates to a kind of foaming PET sheet material section and preparation method thereof, this PET sheet material section is by 100 parts of bottle level PETs, add after 0.1 ~ 5 part of chainextender, 0.1 ~ 10 part of flow improver additive and 0.1 ~ 5 part of oxidation inhibitor mix and extrude pelletizing, more obtained after solid state polymerization thickening.This invention adopts chainextender moderate to be cross-linked PET and forms netted branched structure, increase after molecular chain length through solid-phase tack producing again and improve bottle level PET melt strength, the limiting viscosity that foaming PET sheet material is cut into slices reaches 0.8 ~ 1.2dl/g, melting index MFI=5 ~ 30g/10min.But although the method for passing through to add branching agent in extrusion can improve viscosity or the melt strength of polyester material to a certain extent, but because this branching agent is micromolecular compound mostly, with during polyester macromolecular reaction due to sterically hindered restriction, reaction efficiency can be caused to decline.In addition, the functional group contained due to this micromolecular branching agent is less, to the limited use that the raising of melt strength is played, the polyester material prepared in this way can not be used for the preparation of high magnification foamed polyester materials, can not apply in the preparation of high speed melt-spinning or film.
Summary of the invention
Object of the present invention, improves method of the melt strength of polyester resin and preparation method thereof to provide a kind of exactly.
To achieve these goals, present invention employs following technical scheme: a kind of method improving the melt strength of polyester resin, is characterized in that, comprise the following steps:
A, using the monomer containing active function groups as the first monomer, using another or various of monomer as comonomer, preparation is containing the multipolymer intermediate of active function groups, and the active function groups in this multipolymer intermediate has clear and definite position and quantity;
B, by solution reaction or melt blending reaction, utilize, containing the multipolymer intermediate of active function groups, the molecule of polyester resin is carried out coupling, make polyester macromolecule produce branched structure, thus improve the melt strength of polyester resin.
Described preparation is containing the multipolymer intermediate of active function groups, using the monomer containing active function groups as the first monomer, using another or various of monomer as comonomer, be prepared into the multipolymer intermediate containing active function groups by radical polymerization, letex polymerization, ionic polymerization or polycoordination, and control containing the position of monomer of active function groups and quantity and regulate in the course of the polymerization process.Polymeric type needs to select suitable polymerization methods according to the character of monomer, and prioritizing selection has the polymeric type of controllability on this basis.Polyreaction can be carried out in solution or emulsion according to the type selecting of monomeric species, character and polymerization, also can be undertaken by bulk polymerization, not do concrete restriction.
The structure of described multipolymer intermediate is line style, star-like, combed or dissaving structure.The molecular structure of multipolymer intermediate can be prepared by dissimilar reaction, prepare preferably by modes such as activity/controllable free-radical polymerisation, anionoid polymerization, cationoid polymerisation, general radical polymerizations, preferably activity/controllable free-radical polymerisation, anionoid polymerization, general radical polymerization further, further preferably activity/controllable free-radical polymerisation, anionoid polymerization, most preferably activity/controllable free-radical polymerisation again.The structure of the preferred star-like and combed of the shape of molecule of multipolymer intermediate, most preferably star-like structure.The wherein preferred 2-20 of an arm number arm of star-type polymer, most preferably 3-5 arm.Arm number can make modified polyester resin structure subglobular too much, makes its viscosity degradation; If arm number very little, the effect of coupling can be reduced.
The molecular weight control of multipolymer intermediate is at 100-100, and between 000, preferred molecular weight is between 500-10000, and further preferred molecular weight is between 500-5000, and most preferably molecular weight is between 500-3000.Molecular weight too conference makes polyester material occur to be cross-linked, thus worsens mechanical property and the use properties of polyester modification material, if molecular weight is too little, reduces modified effect.
The described monomer containing active function groups is selected from vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, glycidyl methacrylate, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, one or several in isocyanic ester or acrylate chloride.Preferred use vinylformic acid, maleic anhydride, glycidyl methacrylate, acrylate chloride, preferred maleic anhydride, glycidyl methacrylate, acrylate chloride, most preferably use maleic anhydride further.
Described comonomer is selected from one or more in vinylbenzene, divinyl, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate or butyl methacrylate.The use of comonomer does appropriate selection according to vibrin and the kind containing active function groups monomer, with specific carry out copolymerization containing active function groups monomer time, prioritizing selection uses the comonomer that reactivity ratio (r) is larger.
Can determine according to the molecular structure of multipolymer intermediate and molecular weight containing the monomer of active function groups and the molar ratio of comonomer, for the multipolymer intermediate of molecular weight below 2000, contain the quantity of active function groups monomer in a molecule preferably between 2 ~ 4; For the multipolymer intermediate between molecular weight 2000 ~ 5000, contain the quantity of active function groups monomer in a molecule preferably between 4 ~ 7; For the multipolymer intermediate of molecular weight more than 5000, contain the quantity of active function groups monomer in a molecule preferably more than 5.If molecular weight ratio is comparatively large, and the comparatively small amt of active function groups, the reaction probabilities of active function groups and vibrin end group can be reduced, be unfavorable for linked reaction.For star copolymer intermediate, each arm preferably has one at least containing the monomer of active function groups; For comb copolymer intermediate, each side chain preferably has one at least containing the monomer of active function groups; For linear copolymers intermediate, except meeting except the requirement of molecular weight, the distribution containing active function groups monomer preferably can be evenly distributed in the different positions of multipolymer intermediate molecule chain.
The described position to the monomer containing active function groups and quantity control and regulate, be by adopting the polymerization process of active free radical polymerization, active anionic polymerization or cationoid polymerisation to realize, or adopt adjustment to realize containing the method for the monomer of active function groups and the reactivity ratio of comonomer.
Utilize the multipolymer intermediate containing active function groups that the molecule of polyester resin is carried out coupling described in step B, raw material and the consumption of employing are as follows:
The polyester resin of (1) 100 weight part;
The multipolymer intermediate containing active function groups of (2) 0.1 ~ 20 weight parts;
The catalyzer of (3) 0 ~ 10.0 weight parts but non-vanishing;
Described solution reaction comprises the steps: polyester resin to join in solvent, is progressively warming up to 50 ~ 160 degree, and stirs, and forms the uniform liquid of 5%-15%.Drum nitrogen is got rid of after oxygen, disposablely adds containing active function groups multipolymer intermediate and catalyzer, holding temperature reaction 0.1 ~ 5 hour.After reaction terminates, lowered the temperature by reaction soln, solid is separated out, and after filtration, obtains the branched polyester resinoid after coupling after drying.
In solution reaction, if temperature of reaction is lower than 50 DEG C, polyester material may dissolve not exclusively, makes linked reaction be difficult to carry out.If temperature of reaction is too high, solvent acutely seethes with excitement and linked reaction can not be stablized carry out.
Described melt blending reaction comprise the steps: by dried polyester resin, containing active function groups multipolymer intermediate and catalyzer even in high-speed mixer and mixing, then join in Haake, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, melt blending reaction is carried out at 130 DEG C-350 DEG C, more preferably carry out frit reaction within the scope of 170 DEG C-270 DEG C, reaction times is 1min-30min, more preferably 3min ~ 8min.By product cooling, pelletizing, obtain the branched polyester resinoid after coupling.
In frit reaction, if temperature of reaction is lower than 150 DEG C, polyester can not melting completely, and graft reaction is difficult to carry out.If temperature of reaction is higher than 350 DEG C, not only can increase the side reaction of linked reaction, polyester material also can be made to degrade, worsen its physicals.If the reaction times is less than 1min, graft reaction can not carry out completely, affects the coupling efficiency of polyester.If the reaction times is greater than 30min, then likely make polyester material generation severely degrade.
Described polyester resin comprises linear thermoplastic's resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), poly-hexanodioic acid/butylene terephthalate (PBAT), and poly(lactic acid) (PLA) etc. can the polyester material of complete biodegradable.The performance of polyester material does not do concrete requirement, and the resin for PET class can be a bottle chip level material, fibre-grade material, can be reclaimed materials yet; And can biodegradable resin material can be extrusion grade for PLA class, also can be injection grade.
The molar weight that multipolymer intermediate adds is preferably 0.001: 1 ~ 1: 1 with the ratio of the molar weight of polyester macromolecule, and more preferably 0.01: 1 ~ 1: 1, most preferably be 0.1: 1 ~ 1: 1.The too large or too little melt strength that all can reduce final branched polyester resin product of both add-on ratio.
Described catalyzer comprises antimony-based catalyst, boron series catalysts, Fe-series catalyst, chromium-based catalysts, carboxylate metal salt catalyzer, tin series catalysts, hexamethylenetetramine or quaternary ammonium salt catalyzer.Preferred use tin series catalysts and quaternary ammonium salt catalyzer, most preferably use tin series catalysts.
Described solvent comprises Perfluoroacetone, hexafluoroisopropanol, trifluoroacetic acid, ortho chloro phenol, oil of mirbane, m-methyl phenol or phenol/tetrachloroethane.
The viscosimetric analysis of branched polyester properties of materials:
Branched polyester is fully dissolved in phenol-orthodichlorobenzene mixed solvent, carries out the test of limiting viscosity with standard method.
The mensuration of branched polyester material melt flow rate (MFR):
MFR SRSY-1 melt flow rate (MFR) determinator measures under certain condition according to the kind of polyester material.
The mensuration of branched polyester material storage modulus:
Branched polyester material is placed in the vacuum tabletting machine of certain temperature, and compressing tablet 5-30min makes the thin slice that thickness is about 1mm, then tests its storage modulus with the Rheostress600 rheological analysis instrument that ThermoHaake produces.
The method that the present invention improves the melt strength of polyester resin belongs to the method introducing long-chain branch in extrusion process.In the present invention, the multipolymer intermediate of preparation can be the macromole with specified shape, and the density of active function groups and position can regulate according to actual needs, therefore can be line style, star-like, combed or hyperbranched texture with branched polyester material prepared by this multipolymer intermediate branching agent, and the density of side chain have controllability.Branching molecule due to different texture has different rheological properties, therefore can according to different user demands, and preparation has the polyester macromolecule of different branched structure, be applied to such as foam, the field of melt-spinning or thin film fabrication.
Adopt the present invention to improve the method for the melt strength of polyester resin, greatly can improve the melt strength of polyester resin, the branched polyester material prepared by the inventive method can be applied to foaming, melt-spinning or field of thin film fabrication.
Embodiment
Below by specific embodiment, the invention will be further described.
Embodiment 1:
The multipolymer intermediate of active function groups is contained with maleic anhydride and vinylbenzene two kinds of monomer synthesize, polymerization methods adopts the mode of atom transfer radical polymerization (ATRP), it is wherein solvent with acetone, with ethyl bromide (EPN-Br) for initiator, CuCl is catalyzer, 2,2 '-dipyridyl (bpy) is coordination agent.First by the third toluene, ethyl bromide (EPN-Br), CuCl, 2,2 '-dipyridyl (bpy) joins in there-necked flask, and reaction system is sealed, carry out vacuumizing, inflated with nitrogen, so repeatedly carry out three times, after being warmed up to 40 DEG C, the maleic anhydride acetone soln syringe after refining is squeezed in flask and start reaction, control the add-on of maleic anhydride, make each initiator there is a maleic anhydride molecule, react and add styrene monomer after 8 hours, the molecular weight of vinylbenzene section is set as about 500.Reaction 12 as a child added maleic anhydride monomer again, made with a maleic anhydride molecule on each molecule, and continue reaction and add styrene monomer again after 8 hours, this section of cinnamic molecular weight is also set as 500, keeps reaction 12 hours.Finally add maleic anhydride, make each molecular chain with a maleic anhydride molecule, react and make reaction inactivation after 8 hours, terminate reaction, obtained with three activity anhydride functional groups, and equally distributed styrene-maleic anhydride copolymer intermediate, its molecular weight GPC test result is in table 1.
Get 2 grams of styrene-maleic anhydride copolymer intermediates prepared by aforesaid method, stannous octoate catalyst 0.01 gram, PET resin 50 grams, is fully uniformly mixed.Compound is joined in the Haake torque rheometer being preheating to 270 DEG C, carry out reactive blending with the rotating speed of 80rpm, react and take out product after 5 minutes, carry out analytical test.The properties of branching PET material is listed in table 1.
Reference examples 1:
Contain the multipolymer intermediate of active function groups with maleic anhydride and vinylbenzene two kinds of monomer synthesize, polymerization methods adopts the mode of radical polymerization.Add in constant pressure funnel after the benzoyl peroxide of metering is dissolved with appropriate toluene, the maleic anhydride of metering to be dissolved in appropriate toluene and to join in polymerization reactor, then the vinylbenzene of metering is joined in polymerization reactor stir.Under agitation reaction mixture is slowly heated up, when the temperature of reaction mixture rises to 80-85 DEG C, start to drip the toluene solution being dissolved with benzoyl peroxide.Keep polymerization temperature between 85-90 DEG C, control rate of addition, approximately need 3-4h that initiator benzoyl peroxide solution is added constantly adding along with initiator in polyreaction, continuous adularescent Precipitation in polymerization system, after reaction proceeds to no longer include white precipitate precipitation, the temperature of reaction mixture is down to room temperature, with filter flask elimination solvent toluene.Then at 80 DEG C, vacuum-drying 8h obtains phenylethylene-maleic anhydride white powder multipolymer.The molecular weight of the multipolymer intermediate obtained is listed in table 1.
Get 2 grams of styrene-maleic anhydride copolymer intermediates prepared by aforesaid method, stannous octoate catalyst 0.01 gram, PET resin 50 grams, is fully uniformly mixed.Compound is joined in the Haake torque rheometer being preheating to 270 DEG C, carry out reactive blending with the rotating speed of 80rpm, react and take out product after 5 minutes, carry out analytical test.The properties of branching PET material is listed in table 1.
Embodiment 2:
The polymerization methods of its multipolymer intermediate is identical with embodiment 1, just glycidyl methacrylate is substituted maleic anhydride and is polymerized with styrene monomer as the monomer containing active function groups.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Reference examples 2:
The polymerization methods of its multipolymer intermediate is identical with reference examples 1, just glycidyl methacrylate is substituted maleic anhydride and is polymerized with styrene monomer as the monomer containing active function groups.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Embodiment 3:
The polymerization methods of its multipolymer intermediate is identical with embodiment 1, just methyl methacrylate is substituted vinylbenzene and is polymerized with maleic anhydride monomer as comonomer.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Reference examples 3:
The polymerization methods of its multipolymer intermediate is identical with reference examples 1, just methyl methacrylate is substituted vinylbenzene and is polymerized with maleic anhydride monomer as comonomer.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Embodiment 4:
The polymerization methods of its multipolymer intermediate is identical with embodiment 1, just methyl methacrylate is substituted vinylbenzene and is polymerized with glycidyl methacrylate monomer as comonomer.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Reference examples 4:
The polymerization methods of its multipolymer intermediate is identical with reference examples 2, just methyl methacrylate is substituted vinylbenzene and is polymerized with glycidyl methacrylate monomer as comonomer.It is also identical with embodiment 1 with the coupling method of PET.The molecular weight of multipolymer intermediate and the properties of branching PET are listed in table 1.
Table 1
As can be seen from Table 1, when containing the multipolymer intermediate of active function groups with maleic anhydride and vinylbenzene two kinds of monomer synthesize, no matter adopt which kind of polymerization methods, the melt viscosity of branching PET after coupling can be improved, make melt flow rate (MFR) reach 20-30g/10min, limiting viscosity can bring up to 0.9; And when containing the multipolymer intermediate of active function groups with maleic anhydride and methyl methacrylate two kinds of monomer synthesize, no matter adopt which kind of synthesis mode, the melt flow rate (MFR) of the branching PET product finally obtained is about 10g/10min, and its limiting viscosity brings up to more than 1.0, illustrate and use methyl methacrylate and maleic anhydride as reaction monomers, there is better coupling branching effect.And when using glycidyl methacrylate as reactive monomer, no matter comonomer is adopt vinylbenzene or methyl methacrylate, the multipolymer intermediate obtained all can not improve the melt viscosity of PET.Even when employing radical polymerization mode, during with glycidyl methacrylate and vinylbenzene two kinds of monomer synthesize multipolymer intermediates, the PET product obtained creates DeR, its limiting viscosity only has 0.54, lower than the limiting viscosity of pure PET resin 0.82, this may be due to glycidyl methacrylate non-refractory, create hydrolysis reaction at higher processing temperatures, the hydroxy-acid group produced makes the ester group group of PET matrix there occurs hydrolysis reaction, therefore causes the limiting viscosity of final PET product to reduce.As a whole, the multipolymer intermediate of block type can be obtained by ATRP reaction, this intermediate is lower with steric hindrance during PET macromolecular reaction, the carrying out of linked reaction can be conducive to, therefore as can be seen from Table 1, compared with general radical polymerization, more easily improved the viscosity of PET by the multipolymer intermediate that ATRP reaction is obtained.
Claims (7)
1. improve a method for the melt strength of polyester resin, it is characterized in that, comprise the following steps:
A, using the monomer containing active function groups as the first monomer, using another or various of monomer as comonomer, preparation is containing the multipolymer intermediate of active function groups, and the active function groups in this multipolymer intermediate has clear and definite position and quantity;
B, by solution reaction or melt blending reaction, utilize, containing the multipolymer intermediate of active function groups, the molecule of polyester resin is carried out coupling, make polyester macromolecule produce branched structure, thus improve the melt strength of polyester resin;
Described preparation is containing the multipolymer intermediate of active function groups, using the monomer containing active function groups as the first monomer, using another or various of monomer as comonomer, be prepared into the multipolymer intermediate containing active function groups by radical polymerization, letex polymerization, ionic polymerization or polycoordination, and control containing the position of monomer of active function groups and quantity and regulate in the course of the polymerization process;
The structure of described multipolymer intermediate is line style, star-like, combed or dissaving structure.
2. the method improving the melt strength of polyester resin as claimed in claim 1, it is characterized in that, the described monomer containing active function groups be selected from vinylformic acid, maleic anhydride, methacrylic acid, fumaric acid, methylene-succinic acid, undecylenic acid, acrylamide, N hydroxymethyl acrylamide, Hydroxyethyl acrylate, Propylene glycol monoacrylate, isocyanic ester or acrylate chloride one or several.
3. the method improving the melt strength of polyester resin as claimed in claim 1, it is characterized in that, described comonomer is selected from one or more in vinylbenzene, divinyl, Vinylstyrene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, butyl acrylate or butyl methacrylate.
4. the method improving the melt strength of polyester resin as claimed in claim 1, is characterized in that, utilize the multipolymer intermediate containing active function groups that the molecule of polyester resin is carried out coupling described in step B, raw material and the consumption of employing are as follows:
The polyester resin of (1) 100 weight part;
The multipolymer intermediate containing active function groups of (2) 0.1 ~ 20 weight parts;
The catalyzer of (3) 0 ~ 10.0 weight parts but non-vanishing;
Described solution reaction comprises the steps: polyester resin to join in solvent, progressively heat up, and stir, form the uniform liquid of 5%-15%, after drum nitrogen gets rid of oxygen, disposablely add multipolymer intermediate containing active function groups and catalyzer, holding temperature reaction 0.1 ~ 5 hour, after reaction terminates, reaction soln is lowered the temperature, after filtration, obtain the branched polyester resinoid after coupling after drying;
Described melt blending reaction comprise the steps: by dried polyester resin, containing the multipolymer intermediate of active function groups and catalyzer even in high-speed mixer and mixing, then join in Haake torque rheometer, single screw extrusion machine, twin screw extruder, Banbury mixer, banbury mixers or mill, melt blending reaction is carried out at 130 DEG C-350 DEG C, reaction times is 1min-30min, by product cooling, pelletizing, the branched polyester resinoid after obtained coupling.
5. the method for the melt strength of the raising polyester resin as described in claim 1 or 4, it is characterized in that, described polyester resin comprises polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, poly-hexanodioic acid/mutual-phenenyl two acid bromide two alcohol ester or poly(lactic acid).
6. the method improving the melt strength of polyester resin as claimed in claim 4, it is characterized in that, described catalyzer comprises antimony-based catalyst, boron series catalysts, Fe-series catalyst, chromium-based catalysts, carboxylate metal salt catalyzer, tin series catalysts, hexamethylenetetramine or quaternary ammonium salt catalyzer.
7. the method improving the melt strength of polyester resin as claimed in claim 4, it is characterized in that, described solvent comprises Perfluoroacetone, hexafluoroisopropanol, trifluoroacetic acid, ortho chloro phenol, oil of mirbane, m-methyl phenol or phenol/tetrachloroethane.
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