CN102719009A - Preparation method of modified polypropylene resin for superfine-denier dyeable polypropylene fiber - Google Patents

Abstract

The invention discloses a method for preparing a modified polypropylene resin for superfine-denier dyeable polypropylene, which comprises the following steps: 1) Firstly, by combining melt polycondensation and solid-phase polycondensation, a polycondensate with a melting point of 180-220°C is obtained. Intrinsic viscosity 0.8～1.2dl/g, copolyester additive containing aliphatic dibasic acid and dibasic alcohol; 2) Then, the additive prepared in the above step 1) is compatible with the polyolefin elastomer grafted multi-monomer High-speed spun fine denier polypropylene resin with a melt index of 10-50g/10min, melt blended and granulated in a twin-screw extruder to obtain a dispersed phase with a particle size of less than 1 μm, which is suitable for dyeing of composite spun ultra-fine denier polypropylene Polypropylene resin. The invention has high thermal stability, good spinning processing performance, good dispersion effect of additives in the polypropylene base material, makes the particle size of the dispersed phase less than 1 μm, and satisfies the production of disperse dye-dyeable polypropylene fibers with a fineness less than 0.2dtex.

Description

A kind of preparation method of modified polypropylene resin for superfine denier dyeable polypropylene fiber

technical field

The invention relates to a preparation method of modified polypropylene resin for superfine denier dyeable polypropylene fiber. It belongs to the chemical fiber field.

Background technique

Conventional coarse-denier polypropylene fiber feels waxy, has poor air permeability and moisture absorption, and has no polar groups on the molecular chain of conventional polypropylene, high crystallinity, and poor dyeing performance of polypropylene fiber. to a good promotion. Studies have shown that in addition to the common characteristics of ordinary fine denier fibers such as softness, skin-friendly, and elegant, the fine-denier polypropylene filaments also have good warmth, breathability, moisture conduction, hygiene, and lightness; The dyeable modification of propylene can overcome the disadvantages of the production of polypropylene stock solution dyeing method, such as insufficient color vividness and richness, which cannot be printed, and the color change process consumes a lot of money and the quality is not stable. Therefore, the preparation of dyeable fine-denier and ultra-fine-denier polypropylene fibers has become a research and development hotspot for scientific and technological workers in various countries, and the development of dyeable modified polypropylene resins suitable for the production of fine-denier and ultra-fine-denier dyeable polypropylene fibers is even more critical. Many documents and patents have introduced graft copolymerization of polypropylene and the introduction of dyeing groups for modification, but these methods have the disadvantages of high cost and poor modification effect. And by adding other polymers containing dyeing groups, inorganic nanomaterials, etc. to blend with polypropylene, some progress has been made, such as adding a certain amount of polyamide, polyethylene terephthalate, Polybutylene terephthalate, etc. However, due to the poor compatibility of these polymers with polypropylene, it is difficult to achieve both dyeability, operability and mechanical properties, especially the production of ultrafine denier fibers.

For example, the publication number CN1337424 discloses a "dyeable polypropylene masterbatch and its preparation method", which uses a polyterephthalic acid bis Hydroxyethyl resin, polybishydroxybutyl terephthalate resin, and a certain amount of maleic anhydride and styrene or ethylene copolymer resin are mixed at high speed, and then blended and granulated by an extruder at a certain temperature. Finished masterbatch. By blending and spinning this masterbatch with a certain amount of polypropylene resin, polypropylene fibers that can be deeply dyed with disperse dyes under normal pressure and without a carrier can be obtained.

Publication number CN1339623 discloses a "preparation of dyeable fine-denier polypropylene fiber resin", in which 77-98%wt of polypropylene material that can be spun into fine-denier fiber, 2-20%wt of polyolefin material and 0-3%wt polyolefin derivatives are subjected to binary or ternary melt-blending modification at a temperature of 200-280°C to obtain finished products, which can be used to spin fine-denier fibers that can be dyed by ordinary dyeing processes .

Japanese Patent Application No. 2006-169273 discloses a "dyeable polypropylene resin composition and fibers and nonwoven fabrics made from it", which will be based on polyamides and polyether hindered amines. The electrostatic agent and EVA are mixed in a certain proportion, and then blended with polypropylene in a certain amount, and then melt-spun to obtain fibers that can be dyed with disperse dyes. The fibers have bright color and good washability.

The dyeable polypropylene resin patents disclosed above mainly meet the conventional technical route to prepare dyeable fine-denier polypropylene, and generally the single-filament fineness is greater than 0.5dtex. If you want to produce dyeable fine-denier polypropylene with a smaller single-filament Dispersion and other problems in the polypropylene substrate greatly reduce the spinning performance and mechanical properties, and even cannot be produced normally or the mechanical properties are too poor to have application value.

Contents of the invention

In order to solve the above problems, the object of the present invention is to provide a method for preparing a modified polypropylene resin for ultrafine denier dyeable polypropylene. The present invention has high thermal stability, good spinning performance, and additives in polypropylene substrate The dispersing effect in the medium is good, so that the particle size of the dispersed phase is less than 1 μm, which meets the production of disperse dyeable polypropylene fibers with a fineness less than 0.2dtex.

In order to achieve the above-mentioned purpose, the present invention adopts following technical scheme:

A method for preparing a modified polypropylene resin for superfine-denier dyeable polypropylene, comprising the following steps: 1) Firstly, by combining melt polycondensation and solid-state polycondensation, a compound with a melting point of 180-220°C and an intrinsic viscosity of 0.8- 1.2dl/g, copolyester additive containing aliphatic dibasic acid and dibasic alcohol; 2) Then the additive prepared in step 1) is mixed with the compatibilizer and melt index of polyolefin elastomer grafted multi-monomer Spinning fine-denier polypropylene resin at high speed of 10-50g/10min (purchased from Zhongke Group to produce fine-denier polypropylene resin), melt blending and granulation in twin-screw extruder to obtain dispersed phase particle size less than 1μm, Dyeable polypropylene resin suitable for compound spinning ultrafine denier polypropylene.

Step 1) The preparation steps of co-polyester additives are: using terephthalic acid and ethylene glycol as raw materials, the molar ratio of terephthalic acid and ethylene glycol is 1:1.2, adding aliphatic dibasic acid , one or more of aliphatic dihydric alcohols and aliphatic polyesters, and the added amount accounts for 10-60% of the molar percentage of terephthalic acid. It is synthesized by melt polycondensation with a melting point of 180-220°C and an intrinsic viscosity. 0.4-0.6dl/g copolyester; then the copolyester is subjected to solid-state polycondensation for 24-48 hours at 170-210°C and a vacuum of less than 1kpa to further increase the intrinsic viscosity to 0.8-1.2dl /g.

The aliphatic dibasic acid adopts one of succinic acid, adipic acid and sebacic acid; the aliphatic dibasic alcohol adopts 1,3-propanediol, 1,4-butanediol, 1,6 - one of hexanediol; the aliphatic polyester adopts one of polyethylene adipate, polybutylene adipate and polyhexamethylene adipate with a molecular weight of 1000-3000.

The aliphatic dibasic acid is adipic acid; the aliphatic dibasic alcohol is 1,4-butanediol; the aliphatic polyester is polybutylene adipate.

The preparation step of the dyeable polypropylene resin in the step 2) is: the copolyester additive prepared in the step 1) and the compatibilizer of the polyolefin elastomer grafted multi-monomer, the melt index is 10-50g/10min The polypropylene resin based on additives plus compatibilizer accounts for 5-17% of the total weight percentage of additives, compatibilizer and polypropylene resin, and the amount of compatibilizer added is less than 5% of the total weight percentage of additives, compatibilizer and polypropylene resin, On the twin-screw extruder, melt blending and granulation under the temperature of 200-250 ° C to prepare a dyeable modified polypropylene resin containing additives, the particle size of the dispersed phase is less than 1 μm, suitable for composite spinning ultra-fine denier dyeable Preparation of polypropylene.

The compatibilizer for polyolefin elastomer grafted multi-monomer in the step 2) adopts EPDM-g-MAH (ethylene propylene rubber grafted maleic anhydride), POE-g-(GMA-co-MAH) (poly One of olefin elastomers grafted with glycidyl methacrylate comaleic anhydride). (purchased from Yangzhou Henghui Chemical Co., Ltd.)

The beneficial effects of the present invention are: the present invention adopts copolyester containing aliphatic dibasic acid and dibasic alcohol as additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the melting point difference with polypropylene due to the presence of aliphatic chains. Compatibility, and compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Detailed ways

The present invention will be further described below through specific examples. The test method for the size of the dispersed phase: the blended strip extruded from the twin-screw is brittle in liquid nitrogen, and then the section is analyzed by scanning electron microscopy (SEM), and finally the average particle size is calculated by Photoshop; intrinsic viscosity test Method: According to GB-T 14189-2008, phenol and tetrachloroethane 1:1 were used as solvent for detection.

Example 1

The preparation method of a modified polypropylene resin for ultra-fine denier dyeable polypropylene in this embodiment includes the following steps: 1) Firstly, through the method of combining melt polycondensation and solid-state polycondensation, using terephthalic acid and ethylene glycol as the Raw materials, the molar ratio of terephthalic acid to ethylene glycol is 1:1.2; add 30% of the molar percentage of terephthalic acid and 30% of the molar percentage of terephthalic acid 1,4-butanediol , through the method of melt polycondensation, a copolyester with a melting point of 180°C and an intrinsic viscosity of 0.4dl/g was obtained; then, the copolyester was subjected to solid-state polycondensation at 170°C and a vacuum of less than 1kpa for 36 hours to obtain Copolyester with an intrinsic viscosity of 0.8dl/g and a melting point of 180°C. 2) Then, the copolyester additive with an intrinsic viscosity of 0.8dl/g prepared in step 1) and accounting for 5% of the total weight percentage of the additive, compatibilizer and polypropylene resin is mixed with the total weight percentage of the additive, compatibilizer and polypropylene resin The compatibilizer EPDM-g-MAH of 2% by weight of polyolefin elastomer grafted multi-monomer, the high-speed spinning fine-denier polypropylene resin with melt index of 50g/10min, on the twin-screw extruder, the temperature of 200 ℃ The dyeable modified polypropylene resin containing additives was prepared by melt blending and granulation under the same conditions, and the average particle diameter of the dispersed phase was measured to be 0.87 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 2

The preparation steps of the present embodiment are basically the same as in Example 1, except that the copolyester with an intrinsic viscosity of 0.8dl/g accounting for 10% of the total weight percentage of the additive, compatibilizer and polypropylene resin, accounting for the additive, EPDM-g-MAH with a total weight percentage of 2% of compatibilizer and polypropylene resin and polypropylene resin with a melt index of 50g/10min are blended and granulated at 200°C through a twin-screw extruder, and the particle size of the dispersed phase is measured is 0.92 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness of less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 3

The preparation steps of the present embodiment are basically the same as in Example 1, except that the copolyester with an intrinsic viscosity of 15% of the total weight percentage of the additive, compatibilizer and polypropylene resin is 0.8dl/g, accounting for the additive, EPDM-g-MAH with a total weight percentage of 2% of compatibilizer and polypropylene resin and polypropylene resin with a melt index of 50g/10min are blended and granulated at 220°C through a twin-screw extruder, and the particle size of the dispersed phase is measured is 0.98 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 4

The preparation method of a modified polypropylene resin for ultra-fine denier dyeable polypropylene in this embodiment includes the following steps: 1) Firstly, through the method of combining melt polycondensation and solid-state polycondensation, using terephthalic acid and ethylene glycol as the Raw materials, the molar ratio of terephthalic acid to ethylene glycol is 1:1.2; add 15% adipic acid and 15% 1,4-butanediol in molar percentage of terephthalic acid , through the method of melt polycondensation, a copolyester with a melting point of 220°C and an intrinsic viscosity of 0.6dl/g was obtained; then, the copolyester was subjected to solid-state polycondensation for 36 hours at 190°C and a vacuum degree of less than 1kpa to obtain A copolyester with an intrinsic viscosity of 1.0dl/g and a melting point of 220°C. 2) Then, the copolyester additive with an intrinsic viscosity of 1.0dl/g prepared in step 1) and accounting for 10% of the total weight percentage of the additive, compatibilizer and polypropylene resin is mixed with the total weight percentage of the additive, compatibilizer and polypropylene resin The compatibilizer EPDM-g-MAH of 2% by weight of polyolefin elastomer grafted multi-monomer, the high-speed spinning fine denier polypropylene resin with melt index of 30g/10min, on the twin-screw extruder, the temperature of 230 ℃ The dyeable modified polypropylene resin containing additives was prepared by melt blending and granulation under the same conditions, and the average particle diameter of the dispersed phase was measured to be 0.95 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 5

The preparation method of a modified polypropylene resin for ultra-fine denier dyeable polypropylene in this embodiment includes the following steps: 1) Firstly, through the method of combining melt polycondensation and solid-state polycondensation, using terephthalic acid and ethylene glycol as the Raw materials, the molar ratio of terephthalic acid to ethylene glycol is 1:1.2; adding 6% polybutylene adipate with a molecular weight of 1000 in the molar percentage of terephthalic acid is obtained by melt polycondensation A copolyester with a melting point of 205°C and an intrinsic viscosity of 0.5dl/g; then solid-state polycondensation of the copolyester at 180°C and a vacuum of less than 1kpa for 48 hours to obtain an intrinsic viscosity of 1.2dl/g and a melting point of It is a copolyester at 205°C. 2) Then the copolyester additive with an intrinsic viscosity of 1.2dl/g prepared in step 1) and accounting for 10% of the total weight percentage of the additive, compatibilizer and polypropylene resin is mixed with the total weight percentage of the additive, compatibilizer and polypropylene resin The compatibilizer EPDM-g-MAH of 2% by weight of the polyolefin elastomer grafted multi-monomer, the high-speed spinning fine denier polypropylene resin with a melt index of 10g/10min, on the twin-screw extruder, the temperature of 230°C The dyeable modified polypropylene resin containing additives was prepared by melt blending and granulation under the same conditions, and the average particle diameter of the dispersed phase was measured to be 0.85 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 6

The preparation steps of the present embodiment are basically the same as in Example 1, except that the copolyester with an intrinsic viscosity of 1.2dl/g accounting for 10% of the total weight percentage of additives, compatibilizers and polypropylene resins, accounting for additives, The compatibilizer and polypropylene resin with a total weight percentage of 2% POE-g-(GMA-co-MAH) and polypropylene resin with a melt index of 10g/10min were blended and granulated at 230°C through a twin-screw extruder, and measured The average particle diameter of the obtained dispersed phase was 0.81 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Example 7

The preparation method of a modified polypropylene resin for ultra-fine denier dyeable polypropylene in this embodiment includes the following steps: 1) Firstly, through the method of combining melt polycondensation and solid-state polycondensation, using terephthalic acid and ethylene glycol as the Raw materials, the molar ratio of terephthalic acid to ethylene glycol is 1:1.2; adding 3% polybutylene adipate with a molecular weight of 2000 in the molar percentage of terephthalic acid is obtained by melt polycondensation A copolyester with a melting point of 210°C and an intrinsic viscosity of 0.5dl/g; then solid-state polycondensation of the copolyester at 185°C and a vacuum of less than 1kpa for 36 hours to obtain an intrinsic viscosity of 1.0dl/g and a melting point of It is a copolyester at 205°C. 2) Then, the copolyester additive with an intrinsic viscosity of 1.0dl/g prepared in step 1) and accounting for 10% of the total weight percentage of the additive, compatibilizer and polypropylene resin is mixed with the total weight percentage of the additive, compatibilizer and polypropylene resin Compatibilizer POE-g-(GMA-co-MAH) with 2% by weight of polyolefin elastomer grafted multi-monomer, high-speed spinning fine-denier polypropylene resin with a melt index of 30g/10min, extruded in twin-screw On the machine, under the temperature condition of 230° C., the dyeable modified polypropylene resin containing additives was prepared by melt blending and granulation, and the average particle size of the dispersed phase was measured to be 0.75 μm. The detailed conditions and results are shown in Table 1, which is the preparation process and result display table of the dyeable modified polypropylene resin in the embodiment of the present invention.

In this example, a copolyester containing aliphatic dibasic acid and dibasic alcohol is used as an additive, which can not only reduce the melting point difference between the additive and polypropylene, but also improve the compatibility with polypropylene due to the presence of aliphatic chains. Compared with polyether copolyester, the thermal stability is greatly improved, therefore, the spinning performance is greatly improved. By adopting the method of firstly preparing copolyester with intrinsic viscosity of 0.4-0.6dl/g, and then further increasing the intrinsic viscosity to 0.8-1.2dl/g through solid-state polycondensation, it overcomes various aliphatic dibasic acids and dibasic acids. When the polyalcohol participates in the copolymerization, it is difficult to increase the molecular weight, and it is easy to produce various side reactions, resulting in problems such as a decrease in the quality of the copolyester, so that the copolyester additive has a better viscosity matching with the polypropylene substrate. It is preferred to use a polyolefin elastomer grafted multi-monomer compatibilizer with good compatibility with polypropylene and copolyester, which further improves the dispersion effect of the additive in the polypropylene substrate, and makes the particle size of the dispersed phase The production of disperse dyeable polypropylene with a fineness less than 0.2dtex is less than 1μm, especially the superfine denier dyeable polypropylene produced by composite spinning method (sea-island method, skin-core method, orange segment method, etc.).

Comparative example 1

The preparation steps of this example are basically the same as those of Example 2, except that no compatibilizer is added, the dispersion of the additive in the polypropylene resin is poor, and the measured average particle size of the dispersed phase is 3.75 μm. See Table 1.

Comparative example 2

The preparation steps of this example are basically the same as those of Example 5, except that no compatibilizer is added, the dispersion of the additive in the polypropylene resin is poor, and the measured average particle size of the dispersed phase is 2.95 μm. See 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).