CN102719009A - Preparation method of modified polypropylene resin for superfine-denier dyeable polypropylene fiber - Google Patents
Preparation method of modified polypropylene resin for superfine-denier dyeable polypropylene fiber Download PDFInfo
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- CN102719009A CN102719009A CN2012102095878A CN201210209587A CN102719009A CN 102719009 A CN102719009 A CN 102719009A CN 2012102095878 A CN2012102095878 A CN 2012102095878A CN 201210209587 A CN201210209587 A CN 201210209587A CN 102719009 A CN102719009 A CN 102719009A
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- copolyesters
- polypropylene
- dyeable
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- -1 polypropylene Polymers 0.000 title claims abstract description 129
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 111
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000835 fiber Substances 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 229920001634 Copolyester Polymers 0.000 claims abstract description 78
- 239000000654 additive Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000012071 phase Substances 0.000 claims abstract description 37
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 34
- 238000009987 spinning Methods 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007790 solid phase Substances 0.000 claims abstract description 21
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims description 74
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 44
- 239000004925 Acrylic resin Substances 0.000 claims description 40
- 229920000178 Acrylic resin Polymers 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229920003232 aliphatic polyester Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000986 disperse dye Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000000155 melt Substances 0.000 abstract 2
- 239000000178 monomer Substances 0.000 abstract 1
- 239000012462 polypropylene substrate Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000012545 processing Methods 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 241000675108 Citrus tangerina Species 0.000 description 8
- 150000007520 diprotic acids Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000007086 side reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of modified polypropylene resin for superfine-denier dyeable polypropylene fiber. The preparation method comprises the following steps: 1) first, obtaining copolyester additives which have a melting point of 180 to 220 DEG C and intrinsic viscosity of 0.8 to 1.2dl/g and contain aliphatic dibasic acid and dihydric alcohol, through a combined method of melt polycondensation and solid phase polycondensation; 2) then, granulating the additives prepared in step 1) polyolefin elastomer grafted multi-monomer compatilizers, and high-speed spinning fine denier polypropylene resin with the melt index of 10 to 50g/10min, in a melt blending manner in a double-screw extruder, so as to obtain dyeable polypropylene resin which has a dispersed-phase particle size less than 1 microns and is suitable for composite spinning superfine-denier polypropylene fiber. The modified polypropylene resin has high thermal stability; spun filaments are highly processable; and the additives have a good dispersion effect in polypropylene substrate, so that the dispersed-phase particle size is less than 1 micron. Therefore, dyeable polypropylene fiber for disperse dyes with fineness less than 0.2dtex can be produced.
Description
Technical field
The present invention relates to the preparation method of a kind of super fine denier dyeable polypropylene with modified polypropylene resin.Belong to the man-made fiber field.
Background technology
Conventional thick dawn polypropylene fibre feel is the wax shape, and ventilation property, water absorbability are poor, adds that nonpolarity group on the conventional polypropylene molecular chain, percent crystallinity are high, and the polypropylene fibre dyeing behavior is poor, therefore, in the application of taking, the field is spun by family, can not get excellent popularization all the time.Research shows, the polypropylene filament yarn after the thin dawnization except that the denominator with general fine count fiber as softness, close skin, the advantage such as elegant, also have good warming, breathe freely, lead wet, health, characteristics such as relaxed and comfortable; Polyacrylic dyeable modified, the property bright in luster that exists in the time of then can overcoming polypropylene fibre original liquid coloring method and produce, rich not enough can't stamp processing, and the colour changing process, consumes big, quality and be difficult for deficiencies such as stable.Therefore, the thin dawn super fine denier polypropylene fibre that preparation can be dyed becomes the focus that the various countries scientific worker researchs and develops, and the exploitation of the dyeable modified acrylic resin that wherein suitable thin dawn, super fine denier dyeable polypropylene are produced is crucial especially.A lot of documents and patent have been introduced Vestolen PP 7052 have been carried out graft copolymerization, introduce the method that the dyeing group carries out modification, but these methods exist cost high, deficiencies such as modified effect difference.And also obtained certain progress with polypropylene blending modified research, as add a certain amount of polymeric amide, polyethylene terephthalate, polybutylene terephthalate etc. through adding other polymkeric substance that contains the group that dyes, inorganic nano material etc.But relatively poor because of these polymkeric substance and polyacrylic consistency, be difficult to reach taking into account of dyeability and operability, mechanical property, especially can't satisfy the production of superfine Denier fibre.
Like publication number CN1337424; A kind of " dyeable polypropylene fiber grain and method for making thereof " disclosed; Employing contains the two hydroxyl ethyl ester resins of poly terephthalic acid, the two hydroxy butyl ester resins of poly terephthalic acid of a certain amount of 1.3 1 dicarboxyl Supragil GNs or 1.4 1 dicarboxyl Supragil GNs; With a certain amount of maleic anhydride and vinylbenzene or ethylene copolymer through mixed at high speed, after forcing machine blend granulation at a certain temperature, be the finished product master batch then.With this kind master batch and a certain amount of acrylic resin co-blended spinning, but promptly can obtain the dense polypropylene fibre that dyes of dispersed dye engrain under the normal pressure carrier free state.
Publication number CN1339623; A kind of " preparation of dyable fine denier polypropylene fibre resin " disclosed; Polypropylene material, the polyolefins material of 2～20%wt and the polyolefins verivate of 0～3%wt of the spinned fine count fiber of 77～98%wt are carried out binary or the modification of ternary melt blending under 200～280 ℃ temperature; Make finished product, this finished product can be used to spin the painted fine count fiber of available common dyeing.
The spy opens 2006-169273; A kind of " dyeability profax composition and with its fiber that makes, non-woven " disclosed; To be that basic synthetic meltability permanent anti-static agent and EVA etc. mix in certain proportion with polymeric amide, polyethers hindered amine, by certain addition and polypropene blended, carry out melt-spinning then; Make the fiber of disperse dye dyeable, fiber colour is bright-coloured, washing fastness good.
More than disclosed dyeable polypropylene resin patent; Mainly satisfy routine techniques path of preparing dyeable fine-denier polypropylene; And general filament number is greater than 0.5dtex, as wants the littler dyeable fine-denier polypropylene of manufacture order silk size, understands because of the problems such as dispersiveness of additive in polypropylene base; Spinning properties, mechanical property are descended greatly, in addition can't ordinary production or mechanical property too poor and do not have using value.
Summary of the invention
In order to address the above problem; The object of the present invention is to provide the preparation method of a kind of super fine denier dyeable polypropylene with modified polypropylene resin; The present invention has the thermostability height, and the spinning processing performance is good, and the dispersion effect of additive in polypropylene base is good; The particle diameter that makes disperse phase satisfies the production of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex less than 1 μ m.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A kind of super fine denier dyeable polypropylene is with the preparation method of modified polypropylene resin; Comprise the steps: 1) method that at first combines through melt phase polycondensation and solid phase polycondensation, make fusing point at 180～220 ℃, limiting viscosity 0.8～1.2dl/g, contain the copolyesters additive of aliphatic dibasic acid, divalent alcohol; 2) then with the additive of said step 1) preparation and the how monomeric compatilizer of polyolefin elastomer grafting, melting index high-speed spinning fine denier polypropylene resin (purchase in group of middle section and produce polypropylene dedicated resin of thin dawn) at 10～50g/10min; In the granulation of twin screw extruder melt blending; Make the disperse phase particle diameter less than 1 μ m, be fit to the dyeable polypropylene resin of compound spinning superfine denier polypropylene fibre.
The preparation process of copolyesters additive is in the described step 1): with terephthalic acid, terepthaloyl moietie is raw material; The mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add in aliphatic diprotic acid, aliphatic divalent alcohol and the aliphatic polyester one or more; And add-on accounts for the molar percentage 10～60% of terephthalic acid, and the synthetic fusing point of the method through melt phase polycondensation is at 180～220 ℃, the copolyesters of limiting viscosity 0.4～0.6dl/g; Then with copolyesters under 170～210 ℃, the condition of vacuum tightness less than 1kpa, the solid phase polycondensation through 24～48 hours is further brought up to 0.8～1.2dl/g with limiting viscosity.
Described aliphatic diprotic acid adopts a kind of in Succinic Acid, adipic acid, the sebacic acid; Aliphatic divalent alcohol adopts 1, ammediol, 1, a kind of in 4-butyleneglycol, 1, the 6-hexylene glycol; Aliphatic polyester adopts gathering the adipic acid glycol ester, gather the adipic acid butanediol ester, gathering a kind of in the adipic acid hexylene glycol ester of molecular weight 1000～3000.
Described aliphatic diprotic acid adopts adipic acid; Aliphatic divalent alcohol adopts 1, the 4-butyleneglycol; Aliphatic polyester adopts and gathers the adipic acid butanediol ester.
Described step 2) preparation process of dyeable polypropylene resin is in: with the copolyesters additive and the how monomeric compatilizer of polyolefin elastomer grafting of step 1) preparation; Melting index adds compatilizer at the acrylic resin of 10～50g/10min by additive and accounts for additive, compatilizer and acrylic resin total weight percent 5～17%; And the compatilizer addition is less than additive, compatilizer and acrylic resin total weight percent 5%; On twin screw extruder, melt blending granulation under 200～250 ℃ the temperature condition makes the dyeable modified acrylic resin that contains additive; Its disperse phase particle diameter is fit to the preparation of compound spinning superfine denier dyeable polypropylene less than 1 μ m.
Described step 2) the how monomeric compatilizer of polyolefin elastomer grafting adopts a kind of among EPDM-g-MAH (ethylene-propylene rubber(EPR) grafted maleic anhydride), the POE-g-(GMA-co-MAH) (the common maleic anhydride of polyolefin elastomer graft glycidyl methacrylate) in.(purchasing) in the permanent brightness chemical industry of Yangzhou ltd
Beneficial effect of the present invention is: the present invention adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment
Through specific embodiment, the present invention is done further description below.The testing method of dispersed phase size wherein: the blend batten that will extrude from twin screw, brittle failure in liquid nitrogen is carried out ESEM (SEM) analysis to section then, at last with Photo shop calculating median size; Limiting viscosity testing method: press GB-T 14189-2008, detect as solvent with phenol and tetrachloroethane 1:1.
Embodiment 1
A kind of super fine denier dyeable polypropylene of present embodiment comprises the steps: 1 with the preparation method of modified polypropylene resin) method that at first combines through melt phase polycondensation and solid phase polycondensation; With terephthalic acid, terepthaloyl moietie is raw material, and the mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add molar percentage 30% adipic acid account for terephthalic acid and the molar percentage 30%1 that accounts for terephthalic acid, the 4-butyleneglycol, through the method for melt phase polycondensation, making fusing point and be 180 ℃, limiting viscosity is the copolyesters of 0.4dl/g; Then with this copolyesters 170 ℃, vacuum tightness less than the 1kpa condition under, solid phase polycondensation 36 hours, obtaining limiting viscosity is 0.8dl/g, fusing point is 180 ℃ a copolyesters.2) be 0.8dl/g copolyesters additive and the how monomeric compatilizer EPDM-g-MAH of polyolefin elastomer grafting that accounts for additive, compatilizer and acrylic resin total weight percent 2%, melting index high-speed spinning fine denier polypropylene resin with the limiting viscosity that accounts for additive, compatilizer and acrylic resin total weight percent 5% of said step 1) preparation then at 50g/10min; On twin screw extruder; Melt blending granulation under 200 ℃ the temperature condition; Make the dyeable modified acrylic resin that contains additive, the median size that records disperse phase is 0.87 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 2
The preparation process of present embodiment and embodiment 1 are basic identical; Different is: the acrylic resin of EPDM-g-MAH and melting index 50g/10min that the limiting viscosity that will account for additive, compatilizer and acrylic resin total weight percent 10% is the copolyesters of 0.8dl/g, account for additive, compatilizer and acrylic resin total weight percent 2% is through twin screw extruder; With 200 ℃ of blend granulations, the particle diameter that records disperse phase is 0.92 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 3
The preparation process of present embodiment and embodiment 1 are basic identical; Different is: the acrylic resin of EPDM-g-MAH and melting index 50g/10min that the limiting viscosity that will account for additive, compatilizer and acrylic resin total weight percent 15% is the copolyesters of 0.8dl/g, account for additive, compatilizer and acrylic resin total weight percent 2% is through twin screw extruder; With 220 ℃ of blend granulations, the particle diameter that records disperse phase is 0.98 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 4
A kind of super fine denier dyeable polypropylene of present embodiment comprises the steps: 1 with the preparation method of modified polypropylene resin) method that at first combines through melt phase polycondensation and solid phase polycondensation; With terephthalic acid, terepthaloyl moietie is raw material, and the mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add molar percentage 15% adipic acid account for terephthalic acid and the molar percentage 15%1 that accounts for terephthalic acid, the 4-butyleneglycol, through the method for melt phase polycondensation, making fusing point and be 220 ℃, limiting viscosity is the copolyesters of 0.6dl/g; Then with this copolyesters 190 ℃, vacuum tightness less than the 1kpa condition under, solid phase polycondensation 36 hours, obtaining limiting viscosity is 1.0dl/g, fusing point is 220 ℃ a copolyesters.2) be 1.0dl/g copolyesters additive and the how monomeric compatilizer EPDM-g-MAH of polyolefin elastomer grafting that accounts for additive, compatilizer and acrylic resin total weight percent 2%, melting index high-speed spinning fine denier polypropylene resin with the limiting viscosity that accounts for additive, compatilizer and acrylic resin total weight percent 10% of said step 1) preparation then at 30g/10min; On twin screw extruder; Melt blending granulation under 230 ℃ the temperature condition; Make the dyeable modified acrylic resin that contains additive, the median size that records disperse phase is 0.95 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 5
A kind of super fine denier dyeable polypropylene of present embodiment comprises the steps: 1 with the preparation method of modified polypropylene resin) method that at first combines through melt phase polycondensation and solid phase polycondensation; With terephthalic acid, terepthaloyl moietie is raw material, and the mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add molar percentage 6% molecular weight account for terephthalic acid and be 1000 gather the adipic acid butanediol ester, through the method for melt phase polycondensation, making fusing point and be 205 ℃, limiting viscosity is the copolyesters of 0.5dl/g; Then with this copolyesters 180 ℃, vacuum tightness less than the 1kpa condition under, solid phase polycondensation 48 hours, obtaining limiting viscosity is 1.2dl/g, fusing point is 205 ℃ a copolyesters.2) be 1.2dl/g copolyesters additive and the how monomeric compatilizer EPDM-g-MAH of polyolefin elastomer grafting that accounts for additive, compatilizer and acrylic resin total weight percent 2%, melting index high-speed spinning fine denier polypropylene resin with the limiting viscosity that accounts for additive, compatilizer and acrylic resin total weight percent 10% of said step 1) preparation then at 10g/10min; On twin screw extruder; Melt blending granulation under 230 ℃ the temperature condition; Make the dyeable modified acrylic resin that contains additive, the median size that records disperse phase is 0.85 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 6
The preparation process of present embodiment and embodiment 1 are basic identical; Different is: the POE-g-(GMA-co-MAH) that the limiting viscosity that will account for additive, compatilizer and acrylic resin total weight percent 10% is the copolyesters of 1.2dl/g, account for additive, compatilizer and acrylic resin total weight percent 2% and the acrylic resin of melting index 10g/10min are through twin screw extruder; With 230 ℃ of blend granulations, the median size that records disperse phase is 0.81 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Embodiment 7
A kind of super fine denier dyeable polypropylene of present embodiment comprises the steps: 1 with the preparation method of modified polypropylene resin) method that at first combines through melt phase polycondensation and solid phase polycondensation; With terephthalic acid, terepthaloyl moietie is raw material, and the mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add molar percentage 3% molecular weight account for terephthalic acid and be 2000 gather the adipic acid butanediol ester, through the method for melt phase polycondensation, making fusing point and be 210 ℃, limiting viscosity is the copolyesters of 0.5dl/g; Then with this copolyesters 185 ℃, vacuum tightness less than the 1kpa condition under, solid phase polycondensation 36 hours, obtaining limiting viscosity is 1.0dl/g, fusing point is 205 ℃ a copolyesters.2) be 1.0dl/g copolyesters additive and the how monomeric compatilizer POE-g-of polyolefin elastomer grafting (GMA-co-MAH) that accounts for additive, compatilizer and acrylic resin total weight percent 2%, melting index high-speed spinning fine denier polypropylene resin with the limiting viscosity that accounts for additive, compatilizer and acrylic resin total weight percent 10% of said step 1) preparation then at 30g/10min; On twin screw extruder; Melt blending granulation under 230 ℃ the temperature condition; Make the dyeable modified acrylic resin that contains additive, the median size that records disperse phase is 0.75 μ m.Detailed condition and result see shown in the table 1, and table 1 is the preparation technology of dyeable modified acrylic resin in the embodiment of the invention and indicator gauge as a result.
Present embodiment adopts the copolyesters of fatty family diprotic acid and divalent alcohol as additive; Both can reduce additive and polyacrylic fusing point is poor, because of the existence of aliphatic chain, improve and polyacrylic consistency again; And compare with the polyether-type copolyesters; Thermostability improves greatly, therefore, improves the spinning processing performance greatly.Through taking to make earlier the copolyesters of limiting viscosity 0.4～0.6dl/g; Through solid phase polycondensation, further limiting viscosity is brought up to the method for 0.8～1.2dl/g then, when having overcome multiple aliphatic diprotic acid, divalent alcohol participation copolymerization; Molecular weight is difficult to improve; Be prone to produce various side reactions, cause problems such as copolyesters downgrade, make copolyesters additive and polypropylene base that better viscosity match arranged.The how monomeric compatilizer of polyolefin elastomer grafting that better consistency is preferably all arranged with Vestolen PP 7052 and copolyesters; Further improved the dispersion effect of additive in polypropylene base; The particle diameter that makes disperse phase is less than 1 μ m; Satisfy production, especially composite spinning method (island method, core-skin method, tangerine lobe method etc.) the preparation super fine denier dyeable polypropylene of fiber number less than the disperse dye dyeable polypropylene fibre of 0.2dtex.
Comparative example 1
The preparation process of present embodiment is basic identical with embodiment 2, and different is: do not add compatilizer, and additive dispersed relatively poor in acrylic resin, the median size that records disperse phase is 3.75 μ m.See shown in the table 1.
Comparative example 2
The preparation process of present embodiment is basic identical with embodiment 5, and different is: do not add compatilizer, and additive dispersed relatively poor in acrylic resin, the median size that records disperse phase is 2.95 μ m.See shown in the table 1.
Table 1
Claims (6)
1. a super fine denier dyeable polypropylene is with the preparation method of modified polypropylene resin; It is characterized in that comprising the steps: 1) method that at first combines through melt phase polycondensation and solid phase polycondensation, make fusing point at 180～220 ℃, limiting viscosity 0.8～1.2dl/g, contain the copolyesters additive of aliphatic dibasic acid, divalent alcohol; 2) then with the additive of said step 1) preparation and the how monomeric compatilizer of polyolefin elastomer grafting, melting index high-speed spinning fine denier polypropylene resin at 10～50g/10min; In the granulation of twin screw extruder melt blending; Make the disperse phase particle diameter less than 1 μ m, be fit to the dyeable polypropylene resin of compound spinning superfine denier polypropylene fibre.
2. a kind of super fine denier dyeable polypropylene as claimed in claim 1 is with the preparation method of modified polypropylene resin; The preparation process that it is characterized in that copolyesters additive in the described step 1) is: with terephthalic acid, terepthaloyl moietie is raw material; The mol ratio of terephthalic acid and terepthaloyl moietie is 1:1.2; Add in aliphatic diprotic acid, aliphatic divalent alcohol and the aliphatic polyester one or more; And add-on accounts for the molar percentage 10～60% of terephthalic acid, and the synthetic fusing point of the method through melt phase polycondensation is at 180～220 ℃, the copolyesters of limiting viscosity 0.4～0.6dl/g; Then with copolyesters under 170～210 ℃, the condition of vacuum tightness less than 1 kpa, the solid phase polycondensation through 24～48 hours is further brought up to 0.8～1.2dl/g with limiting viscosity.
3. a kind of super fine denier dyeable polypropylene as claimed in claim 1 is characterized in that with the preparation method of modified polypropylene resin: described aliphatic diprotic acid adopts a kind of in Succinic Acid, adipic acid, the sebacic acid; Aliphatic divalent alcohol adopts 1, ammediol, 1, a kind of in 4-butyleneglycol, 1, the 6-hexylene glycol; Aliphatic polyester adopts gathering the adipic acid glycol ester, gather the adipic acid butanediol ester, gathering a kind of in the adipic acid hexylene glycol ester of molecular weight 1000～3000.
4. a kind of super fine denier dyeable polypropylene as claimed in claim 3 is characterized in that with the preparation method of modified polypropylene resin: described aliphatic diprotic acid adopts adipic acid; Aliphatic divalent alcohol adopts 1, the 4-butyleneglycol; Aliphatic polyester adopts and gathers the adipic acid butanediol ester.
5. a kind of super fine denier dyeable polypropylene as claimed in claim 1 is with the preparation method of modified polypropylene resin; It is characterized in that: the preparation process of dyeable polypropylene resin is described step 2): with the copolyesters additive and the how monomeric compatilizer of polyolefin elastomer grafting of step 1) preparation; Melting index adds compatilizer at the acrylic resin of 10～50g/10min by additive and accounts for additive, compatilizer and acrylic resin total weight percent 5～17%; And the compatilizer addition is less than additive, compatilizer and acrylic resin total weight percent 5%; On twin screw extruder; Melt blending granulation under 200～250 ℃ the temperature condition makes the dyeable modified acrylic resin that contains additive, and its disperse phase particle diameter is less than 1 μ m.
6. a kind of super fine denier dyeable polypropylene as claimed in claim 5 is characterized in that with the preparation method of modified polypropylene resin: a kind of described step 2) among the how monomeric compatilizer of polyolefin elastomer grafting employing EPDM-g-MAH, the POE-g-(GMA-co-MAH).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641164A (en) * | 2018-05-11 | 2018-10-12 | 江苏奥神新材料股份有限公司 | A kind of super fine denier polyimides chopped strand improved polyalkene and preparation method thereof |
| CN109487364A (en) * | 2017-09-11 | 2019-03-19 | 东丽纤维研究所（中国）有限公司 | One kind can contaminate polyolefine fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103440A (en) * | 1993-12-01 | 1995-06-07 | 北京服装学院 | Method for mfg. disperse dye dyeable polypropylene fibre |
| CN1339623A (en) * | 2000-08-23 | 2002-03-13 | 东华大学 | Preparation of resin specially for dyable fine denier polypropylene fibre |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103440A (en) * | 1993-12-01 | 1995-06-07 | 北京服装学院 | Method for mfg. disperse dye dyeable polypropylene fibre |
| CN1339623A (en) * | 2000-08-23 | 2002-03-13 | 东华大学 | Preparation of resin specially for dyable fine denier polypropylene fibre |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109487364A (en) * | 2017-09-11 | 2019-03-19 | 东丽纤维研究所（中国）有限公司 | One kind can contaminate polyolefine fiber |
| CN109487364B (en) * | 2017-09-11 | 2021-09-28 | 东丽纤维研究所（中国）有限公司 | Dyeable polyolefin fiber |
| CN108641164A (en) * | 2018-05-11 | 2018-10-12 | 江苏奥神新材料股份有限公司 | A kind of super fine denier polyimides chopped strand improved polyalkene and preparation method thereof |
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