CN109401215B - Polyester composition and non-woven fabric, and preparation method and application thereof - Google Patents
Polyester composition and non-woven fabric, and preparation method and application thereof Download PDFInfo
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- CN109401215B CN109401215B CN201710703774.4A CN201710703774A CN109401215B CN 109401215 B CN109401215 B CN 109401215B CN 201710703774 A CN201710703774 A CN 201710703774A CN 109401215 B CN109401215 B CN 109401215B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
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Abstract
Hair brushThe invention relates to the field of polymers, and discloses a polyester composition and a preparation method thereof, a non-woven fabric and a preparation method thereof, and applications of the non-woven fabric and the non-woven fabric. Specifically, the polyester composition comprises the following components by taking the total weight of the components as a reference: (1)51-99 wt% of a polyester A, the polyester A being a copolymer comprising a repeating unit A represented by formula (I) and a repeating unit B represented by formula (II); (2)1 to 49% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II). The non-woven fabric made of the polyester composition of the present invention has good water absorption, air permeability and sterilization, and particularly, the non-woven fabric of the present invention can be sterilized in hot water (e.g., 100 ℃) and greatly shrunk, thus being easily compressed to a small volume, facilitating the recovery and reproduction of materials.
Description
Technical Field
The invention relates to the field of polymers, in particular to a polyester composition, a preparation method of the polyester composition, a non-woven fabric, a preparation method of the non-woven fabric and application of the non-woven fabric and the non-woven fabric.
Background
The non-woven fabric is also called non-woven fabric, and is a fabric formed without spinning woven fabric, and is formed by that textile short fibers or filaments are directionally or randomly arranged to form a fiber web structure, and then the fiber web structure is reinforced by adopting a mechanical method, a thermal bonding method or a chemical method. At present, disposable textile products, in particular disposable medical textile products, are mainly made of non-woven fabrics.
Disposable surgical gowns represent a large area of application for nonwoven fabrics in the medical disposable product market. The materials of the common disposable surgical gown on the market at present are as follows: (1) the polypropylene wood pulp composite spunlaced nonwoven fabric has enough breaking tensile strength, abrasion resistance and continuous antibacterial performance as described in CN205800418U, and the wood pulp paper layer improves the moisture absorption and air permeability of the product. (2) Polypropylene, polyhydroxybutyrate and polylactic acid multilayer composite materials, as described in CN204398434U and CN105054444A, the degradable, flame retardant and antistatic nonwoven fabric for surgical gowns comprises: the first base cloth layer, the heat insulation layer, the waterproof layer, the activated carbon adsorption layer and the second base cloth layer are sequentially bonded from bottom to top; wherein the first base cloth layer is formed by criss-cross arrangement of composite fibers formed by melting and spinning polyhydroxybutyrate and polylactic acid; the second base cloth layer is formed by staggered arrangement of composite fibers formed by melting and spinning polypropylene and modified polyacrylonitrile; a plurality of through holes are distributed on the surfaces of the first base cloth layer and the second base cloth layer. The inner layer of the non-woven fabric of the operating coat is degradable, has good flame retardant, moisture absorption and ventilation functions, and is high in strength and comfortable to wear. (3) The polyethylene film and SMS nonwoven fabric composite material, as described in CN204317582U, is lined with a double-layer structure of SMS composite nonwoven fabric and polyethylene film. (4) Nonwoven fabrics with resin reinforcement, as mentioned in CN105015128B, are used as reinforcement material for surgical gowns to protect patients and medical staff from cross infection. The disposable surgical gown reinforcing sheet material comprises a base cloth layer and a reinforcing layer, wherein an adhesion group is arranged between the base cloth layer and the reinforcing layer, and the reinforcing layer comprises polyethylene, polypropylene and the like. Surgical gowns are a large area of application for nonwoven fabrics in the medical disposable product market. The disposable operation protective clothing becomes medical waste after being used in one operation. According to the medical waste management regulation published by the State Council of the people's republic of China in 2003, medical waste is required to be sent to a special medical waste disposal center for centralized disposal, and then is incinerated, sterilized and then buried or destroyed. When the waste operation protective clothing is subjected to incineration treatment, coal and electric energy sources are consumed, and waste gas is removed; the residue after incineration needs to be buried. The disposal of medical waste can therefore lead to secondary pollution. Most of the materials on the market are difficult to recycle. Therefore, how to conveniently recycle the disposable medical textile product becomes a very urgent problem.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art by providing a polyester composition, a process for the preparation of the polyester composition, a nonwoven fabric, a process for the preparation thereof, and their use. The non-woven fabric prepared from the polyester composition has good water absorption, air permeability and sterilization easiness, particularly, the non-woven fabric can be sterilized in hot water (such as 100 ℃) and greatly shrunk, so that the non-woven fabric can be easily compressed to a small volume, the recovery and reproduction of materials (particularly disposable materials) are convenient, and the re-produced non-woven fabric has similar performance to the non-woven fabric used for the first time, is suitable to be continuously used as a raw material of disposable non-woven fabric products (particularly disposable medical textile products), so that the problem of recycling of materials is well solved.
In order to achieve the above object, in a first aspect, the present invention provides a polyester composition, wherein the polyester composition comprises the following components, based on the total weight of the components:
(1)51 to 99% by weight of a polyester A which is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II) and which is contained in an amount of 75 to 99 mol%, preferably 81 to 95 mol%, and a repeating unit B contained in an amount of 1 to 25 mol%, preferably 5 to 19 mol%, based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A,
Wherein m1 is an integer of 2-4, n1 is an integer of 2-4, m1 and n1 are the same or different, and the weight-average molecular weight of the polyester A is 50,000-900,000;
(2)1 to 49% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit C is 20 to 74 mol%, preferably 40 to 70 mol%, and the content of the repeating unit B is 26 to 80 mol%, preferably 30 to 60 mol%, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
wherein m2 is an integer of 2 to 4, n2 is an integer of 2 to 4, m2 and n2 are the same or different, and the weight-average molecular weight of the polyester B is 50,000-900,000.
In a second aspect, the present invention also provides a preparation method of the above polyester composition, wherein the preparation method comprises: the polyester A and the polyester B are blended, and the obtained mixture is extruded and granulated.
In a third aspect, the invention also provides a non-woven fabric, wherein the non-woven fabric contains the polyester composition and/or the polyester composition obtained by the preparation method.
In a fourth aspect, the present invention also provides a method for preparing a nonwoven fabric, the method comprising: the polyester composition and/or the polyester composition obtained by the preparation method are spun-bonded to prepare a non-woven fabric.
In a fifth aspect, the invention also provides the polyester composition, the polyester composition obtained by the preparation method, the non-woven fabric and the application of the non-woven fabric obtained by the preparation method in non-woven fabric products, preferably in disposable non-woven fabric products, and more preferably in disposable medical non-woven fabric products.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a polyester composition, wherein the polyester composition comprises the following components, based on the total weight of the components:
(1)51 to 99% by weight of a polyester A which is a copolymer comprising a repeating unit A represented by the formula (I) and a repeating unit B represented by the formula (II) and which is contained in an amount of 75 to 99 mol%, preferably 81 to 95 mol%, and a repeating unit B contained in an amount of 1 to 25 mol%, preferably 5 to 19 mol%, based on the total number of moles of the repeating unit A and the repeating unit B in the polyester A,
Wherein m1 is an integer from 2 to 4; n1 is an integer from 2 to 4, preferably 2; and m1 and n1 are the same or different, the weight average molecular weight of the polyester A is 50,000-900,000, preferably 100,000-500,000;
(2)1 to 49 wt% of polyester B, the polyester B is a copolymer containing a repeating unit C shown in a formula (III) and a repeating unit B shown in a formula (II), the content of the repeating unit C is 20 to 74 mol%, preferably 40 to 70 mol%, and the content of the repeating unit B is 26 to 80 mol%, preferably 30 to 60 mol% based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
wherein m2 is an integer from 2 to 4; n2 is an integer from 2 to 4, preferably 2; and m2 and n2 are the same or different; the weight average molecular weight of the polyester B is 50,000-900,000, preferably 100,000-500,000.
In the present invention, m1 and m2 may be the same or different, and n1 and n2 may be the same or different. However, when m1 and m2 are the same and n1 and n2 are the same, the content of the repeating unit B in the polyester A is different from that in the polyester B.
In the present invention, the weight average molecular weight of the polymer is measured according to Gel Permeation Chromatography (GPC).
Preferably, the polyester composition comprises 55 to 70 wt.% of polyester A and 30 to 45 wt.% of polyester B. In the present invention, the composition of the polymer is determined by the amount of the raw materials charged.
In the present invention, the polyester a and the polyester B may be at least one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, and preferably a random copolymer and/or a block copolymer. The sources of the polyester A and the polyester B are not particularly limited in the present invention, and the polyester A and the polyester B can be obtained by a conventional means in the field, can be obtained commercially, or can be prepared according to the method disclosed in example B13-B21 in CN 100429256C. Specifically, the preparation method of the polyester A comprises the following steps:
(1) reacting a monomer A and a monomer B in the presence of a first catalyst in an inert atmosphere;
(2) reacting a monomer C and a monomer D in the presence of a first catalyst in an inert atmosphere;
(3) reacting the reaction product obtained in the step (1) and the reaction product obtained in the step (2) in the presence of a second catalyst;
wherein the monomer A is butanediol; the monomer B is terephthalic acid and/or ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; the monomer C is dihydric alcohol (especially saturated straight chain dihydric alcohol) of C2-C4; the monomer D is dibasic acid (especially saturated straight chain dibasic acid) of C4-C6; the first catalyst is at least one of tetrabutyl titanate, titanium dioxide, diethoxy titanium and zinc acetate, and tetrabutyl titanate is preferred; the second catalyst is at least one of lanthanum acetylacetonate, lanthanum trichloride, triphenoxy lanthanum and lanthanum propionate, and is preferably lanthanum acetylacetonate.
In the present invention, in step (1), the molar ratio of the monomer B to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In the present invention, in the step (2), the molar ratio of the monomer D to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In a preferred case, the molar ratio of the total amount of the first catalyst (sum of the amounts of the first catalyst used in step (1) and step (2)) to the amount of the second catalyst is 1: 0.5-1.5, preferably 1: 0.8-1.2.
In the present invention, the types of the respective reaction monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of the respective repeating units in the product can be controlled by adjusting the amount and ratio of the charge.
In the present invention, in step (1), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in the step (2), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in the step (3), the temperature of the reaction is preferably 180-240 ℃.
In a preferred embodiment of the present invention, when m1 is 4, the preparation method of the polyester A comprises the following steps:
(S1) reacting butanediol and monomer a' in the presence of a first catalyst in an inert atmosphere;
(S2) reacting the reaction product obtained from the step (S1) with a monomer B' in the presence of a second catalyst;
wherein A' is terephthalic acid and/or an ester thereof, preferably at least one of terephthalic acid, dimethyl terephthalate and diethyl terephthalate; the monomer B' is dibasic acid (especially saturated straight chain dibasic acid) of C4-C6; the first catalyst and the second catalyst are as described above and will not be described in detail herein.
In the present invention, in the step (S1), the molar ratio of the monomer a' to the first catalyst is 1: 0.0001-0.02: 0.0001-0.02, more preferably 1: 0.001-0.003: 0.001-0.003.
In a preferred case, the molar ratio of the amount of the first catalyst to the amount of the second catalyst is 1: 0.5-1.5, preferably 1: 0.8-1.2.
In the present invention, the types of the respective reaction monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of the respective repeating units in the product can be controlled by adjusting the amount and ratio of the charge.
In the present invention, in the step (S1), the temperature of the reaction is preferably 160-220 ℃; in the present invention, in the step (S2), the temperature of the reaction is preferably 180-240 ℃.
According to the present invention, the polyester B can be prepared according to the above-mentioned preparation method of the polyester A, wherein the types of the respective reaction monomers can be adjusted correspondingly according to the composition and molecular weight of the target product, and the molecular weight of the product and the content of the respective repeating units in the product can be controlled by adjusting the amount and ratio of the charged materials to obtain the polyester B.
According to the invention, the polyester composition may also contain auxiliary fillers; preferably, the auxiliary filler is present in an amount of 0.1 to 25 wt%, more preferably 1 to 20 wt%, based on the total weight of the polyester composition.
According to the present invention, the auxiliary filler has the effects of accelerating the spinning, curing and forming of the composition, adjusting the mechanical strength of the fabric or nonwoven fabric, improving the flame retardancy and oxidation resistance of the article, adjusting the color and gloss of the article, and may be conventionally selected in the art, for example, the auxiliary filler may be at least one selected from the group consisting of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylate, metal phosphate, tetrabromobisphenol a, decabromodiphenyl ether, hexabromocyclododecane, low density polyethylene, polyphosphate, phosphite, hindered phenol, hindered amine, dibenzyl sorbitol and its derivatives, hyperbranched polyamide, and ethylene-methacrylic acid ionomer; preferably at least one of hindered phenols, calcium carbonate, carbon black, erucamide, titanium dioxide, tris (2, 3-dibromopropyl) phosphate (TDBPP), low density polyethylene, and hyperbranched polyamides.
In a second aspect, the present invention also provides a preparation method of the above polyester composition, wherein the preparation method comprises: the polyester A and the polyester B are blended, and the obtained mixture is extruded and granulated.
In the preparation method of the polyester composition of the present invention, the composition of the polyester a, the composition of the polyester B, and the amounts of the polyester a and the polyester B are as described above, and are not described herein again.
According to the present invention, the preparation method may further include: the blending is carried out in the presence of an auxiliary filler; preferably, the auxiliary filler is present in an amount of 0.1 to 25 wt%, more preferably 1 to 20 wt%, based on the total weight of the polyester composition.
In the method for preparing the polyester composition of the present invention, the kind of the auxiliary filler is as described above, and will not be described herein again.
In the present invention, the inventors have unexpectedly found during the research that: the polyester A has good compatibility with the polyester B, and therefore, a compatibilizer may not be added during blending. The compatibilizer is a substance conventionally used in the art to improve compatibility of blending raw materials, and may be, for example, at least one of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH, and PP-g-MAH.
According to the invention, the blending process can be carried out under stirring. In the present invention, the stirring conditions are not particularly limited as long as the raw materials can be uniformly mixed, and in a preferable case, the stirring speed is 20 to 150r/min, and the stirring time is 5 to 15 min.
According to the present invention, the extrusion granulation process may be performed according to a conventional extrusion granulation method, for example, the extrusion granulation may be performed in a twin-screw extruder. In a preferred case, the temperature of the extrusion granulation is 140-.
In a third aspect, the present invention also provides a nonwoven fabric, wherein the nonwoven fabric comprises the polyester composition and/or the polyester composition obtained by the preparation method, i.e., the nonwoven fabric is prepared from the polyester composition and/or the polyester composition obtained by the preparation method.
In the present invention, the filament diameter of the nonwoven fabric may be 5 to 100. mu.m, preferably 20 to 50 μm.
In a fourth aspect, the present invention also provides a method for preparing a nonwoven fabric, the method comprising: the polyester composition and/or the polyester composition obtained by the preparation method are spun-bonded to prepare a non-woven fabric. The apparatus used in the spunbonding process of the present invention is not particularly limited, and for example, a spunbond machine conventionally used in the art may be used.
In preferred aspects, the spunbonding process comprises processes of extrusion, spinning, netting and consolidation. More preferably, the extrusion process comprises three temperature zones, wherein the temperature of the first temperature zone is 140-; the temperature of the second temperature zone is 150-260 ℃, preferably 165-220 ℃; the temperature of the third temperature zone is 170-260 ℃, and preferably 180-230 ℃.
In the present invention, the spinning conditions are not particularly limited, for example, the spinning temperature may be 150-; the spinning rate may be 10-40r/min, preferably 15-30 r/min.
In the present invention, the condition of the web formation is not particularly limited, and for example, the rate of the web formation may be 5 to 30r/min, preferably 10 to 20 r/min.
In the invention, the reinforcement is preferably carried out by hot rolling at a temperature of 80-170 ℃, preferably 90-120 ℃.
In a fifth aspect, the invention also provides the polyester composition, the polyester composition obtained by the preparation method, the non-woven fabric and the application of the non-woven fabric obtained by the preparation method in non-woven fabric products, preferably in disposable non-woven fabric products, and more preferably in disposable medical non-woven fabric products.
Preferably, the disposable medical non-woven fabric article is selected from at least one of a disposable surgical gown, a disposable medical mask, a disposable medical cap, a disposable medical sheet and a disposable surgical hole towel.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the weight average molecular weight of the polymer was measured using Gel Permeation Chromatography (GPC) with Tetrahydrofuran (THF) as a solvent on a Waters-208 (with a Waters 2410RI detector, 1.5mL/min flow rate, 30 ℃) instrument calibrated with styrene standards;
the composition of the polyester composition is determined by the feeding of raw materials;
the polyester used in the present invention is prepared by itself in accordance with the method disclosed in example B13-B21 in CN100429256C, wherein the molecular weight of the product and the content of each repeating unit in the product can be controlled by adjusting the amount and ratio of the raw materials of the reaction according to the composition and molecular weight of the target product.
Example 1
This example is provided to illustrate the nonwoven fabric and the method of making the same.
Under the condition of stirring (the stirring speed is 30r/min, the stirring time is 10min), 3kg of terephthalic acid butanediol-succinic acid butanediol copolyester A (the weight-average molecular weight is 120,000, wherein the total mole number of a terephthalic acid butanediol repeating unit and a succinic acid butanediol repeating unit is taken as a reference, the content of the terephthalic acid butanediol repeating unit is 18 mol%), 2kg of terephthalic acid butanediol-succinic acid butanediol copolyester B (the weight-average molecular weight is 100,000, wherein the total mole number of the terephthalic acid butanediol repeating unit and the succinic acid butanediol repeating unit is taken as a reference, the content of the terephthalic acid butanediol repeating unit is 50 mol%), 0.25kg of antioxidant 300 (hindered phenol antioxidant produced by chemical engineering department material synthesis research, the following steps are carried out), mixing, extruding by an extruder, extruding by a screw extruder, and extruding by a screw extruder, Drawing, air cooling and granulating, wherein the temperature of each section from the feed inlet to the extrusion outlet in the twin-screw extruder is 170 ℃, 180 ℃, 185 ℃, 190 ℃ and 190 ℃ in sequence. Polyester composition A1 was obtained.
The polyester polymer A1 is added into a screw of a spun-bond machine, the temperature of a first zone of the screw is 185 ℃, the temperature of a second zone of the screw is 190 ℃, the temperature of a third zone of the screw is 205 ℃, the spinning temperature is 195 ℃, the rotating speed of a metering pump is 20r/min, the net forming speed is 17m/min, and the hot rolling temperature is 105 ℃, so that the non-woven fabric B1 is obtained.
Example 2
This example is provided to illustrate the nonwoven fabric and the method of making the same.
Under the condition of stirring (the stirring speed is 30r/min, the stirring time is 10min), 3.5kg of terephthalic acid butanediol-succinic acid butanediol copolyester A (the weight-average molecular weight is 120,000, wherein the total mole number of a terephthalic acid butanediol repeating unit and a succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 5 mol%), 1.5kg of terephthalic acid butanediol-succinic acid butanediol copolyester B (the weight-average molecular weight is 100,000, wherein the total mole number of the terephthalic acid butanediol repeating unit and the succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 60 mol%), 0.25kg of antioxidant 300 are mixed and then extruded, drawn, cooled by air and cut into granules by a double-screw extruder, wherein the temperature of each section from a feed inlet to an extrusion outlet in the double-screw extruder is 170 ℃ in sequence, 180 ℃, 185 ℃, 190 ℃ and 190 ℃. Polyester composition A2 was obtained.
The polyester polymer A2 is added into a screw of a spun-bonding machine, the temperature of a first area of the screw is 185 ℃, the temperature of a second area of the screw is 190 ℃, the temperature of a third area of the screw is 205 ℃, the spinning temperature is 195 ℃, the rotating speed of a metering pump is 20r/min, the web forming speed is 17m/min, and the hot rolling temperature is 105 ℃, so that the non-woven fabric B2 is obtained.
Example 3
This example is provided to illustrate the nonwoven fabric and the method of making the same.
Under the condition of stirring (the stirring speed is 30r/min, the stirring time is 10min), 2.75kg of terephthalic acid butanediol-succinic acid butanediol copolyester A (the weight-average molecular weight is 120,000, wherein the total mole number of a terephthalic acid butanediol repeating unit and a succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 12 mol%), 2.25kg of terephthalic acid butanediol-succinic acid butanediol copolyester B (the weight-average molecular weight is 100,000, wherein the total mole number of the terephthalic acid butanediol repeating unit and the succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 30 mol%), 0.25kg of antioxidant 300 are mixed and then extruded, drawn, cooled by air and cut into granules by a double-screw extruder, wherein the temperature of each section from a feed inlet to an extrusion outlet in the double-screw extruder is 170 ℃ in sequence, 180 ℃, 185 ℃, 190 ℃ and 190 ℃. Polyester composition A3 was obtained.
The polyester polymer A3 is added into a screw of a spun-bonding machine, the temperature of a first area of the screw is 185 ℃, the temperature of a second area of the screw is 190 ℃, the temperature of a third area of the screw is 205 ℃, the spinning temperature is 195 ℃, the rotating speed of a metering pump is 20r/min, the web forming speed is 17m/min, and the hot rolling temperature is 105 ℃, so that the non-woven fabric B3 is obtained.
Example 4
This example is provided to illustrate the nonwoven fabric and the method of making the same.
Under the condition of stirring (the stirring speed is 30r/min, the stirring time is 10min), 4.95kg of terephthalic acid butanediol-succinic acid butanediol copolyester A (the weight-average molecular weight is 120,000, wherein the total mole number of a terephthalic acid butanediol repeating unit and a succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 25 mol%), 0.05kg of terephthalic acid butanediol-succinic acid butanediol copolyester B (the weight-average molecular weight is 100,000, wherein the total mole number of the terephthalic acid butanediol repeating unit and the succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 80 mol%), 0.25kg of antioxidant 300 are mixed and then extruded, drawn, cooled by air and cut into granules by a double-screw extruder, wherein the temperature of each section from a feed inlet to an extrusion outlet in the double-screw extruder is 170 ℃ in sequence, 180 ℃, 185 ℃, 190 ℃ and 190 ℃. Polyester composition A4 was obtained.
The polyester polymer A4 is added into a screw of a spun-bonding machine, the temperature of a first area of the screw is 185 ℃, the temperature of a second area of the screw is 190 ℃, the temperature of a third area of the screw is 205 ℃, the spinning temperature is 195 ℃, the rotating speed of a metering pump is 20r/min, the web forming speed is 17m/min, and the hot rolling temperature is 105 ℃, so that the non-woven fabric B4 is obtained.
Example 5
This example is provided to illustrate the nonwoven fabric and the method of making the same.
Under the condition of stirring (the stirring speed is 30r/min, the stirring time is 10min), 2.55kg of terephthalic acid butanediol-succinic acid butanediol copolyester A (the weight-average molecular weight is 120,000, wherein the total mole number of a terephthalic acid butanediol repeating unit and a succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 1 mol percent), 2.45kg of terephthalic acid butanediol-succinic acid butanediol copolyester B (the weight-average molecular weight is 100,000, wherein the total mole number of the terephthalic acid butanediol repeating unit and the succinic acid butanediol repeating unit is taken as the reference, the content of the terephthalic acid butanediol repeating unit is 26 mol percent), 0.25kg of antioxidant 300 are mixed and then extruded, drawn, cooled by air and cut into granules by a double-screw extruder, wherein the temperature of each section from a feed inlet to an extrusion outlet in the double-screw extruder is 170 ℃ in sequence, 180 ℃, 185 ℃, 190 ℃ and 190 ℃. Polyester composition A5 was obtained.
The polyester polymer A5 is added into a screw of a spun-bonding machine, the temperature of a first area of the screw is 185 ℃, the temperature of a second area of the screw is 190 ℃, the temperature of a third area of the screw is 205 ℃, the spinning temperature is 195 ℃, the rotating speed of a metering pump is 20r/min, the web forming speed is 17m/min, and the hot rolling temperature is 105 ℃, so that the non-woven fabric B5 is obtained.
Example 6
This example is provided to illustrate the nonwoven fabric and the method of making the same.
The procedure is as in example 1, except that polyester A is a butylene terephthalate-butylene adipate copolyester (weight average molecular weight 120,000, wherein the content of butylene terephthalate repeat units is 18 mole%, based on the total moles of butylene terephthalate repeat units and butylene adipate repeat units); polyester B was a butylene terephthalate-butylene adipate copolyester (weight average molecular weight 100,000, wherein the content of butylene terephthalate repeat units was 50 mole%, based on the total number of moles of butylene terephthalate repeat units and butylene adipate repeat units). Polyester composition A6 and nonwoven B6 were obtained.
Example 7
This example is provided to illustrate the nonwoven fabric and the method of making the same.
The procedure was followed as in example 1, except that polyester A was butylene terephthalate-ethylene succinate copolyester (weight average molecular weight 200,000, in which the content of butylene terephthalate repeat units was 18 mol%, based on the total number of moles of butylene terephthalate repeat units and ethylene succinate repeat units); the polyester B was butylene terephthalate-ethylene succinate copolyester (weight average molecular weight 200,000, wherein the content of butylene terephthalate repeat units was 50 mol%, based on the total number of moles of butylene terephthalate repeat units and ethylene succinate repeat units). Polyester composition A7 and nonwoven B7 were obtained.
Example 8
This example is provided to illustrate the nonwoven fabric and the method of making the same.
The procedure is as in example 1, except that polyester A is a butylene terephthalate-butylene glycol adipate copolyester (weight average molecular weight 500,000, wherein the content of butylene terephthalate repeat units is 18 mole%, based on the total moles of butylene terephthalate repeat units and butylene glycol oxalate repeat units); the polyester B was butylene terephthalate-ethylene succinate copolyester (weight average molecular weight 500,000, wherein the content of butylene terephthalate repeat units was 50 mol%, based on the total number of moles of butylene terephthalate repeat units and ethylene succinate repeat units). Polyester composition A8 and nonwoven B8 were obtained.
Example 9
This example is provided to illustrate the nonwoven fabric and the method of making the same.
The procedure of example 1 was followed except that 0.25kg of titanium dioxide of the same weight was used instead of 0.25kg of the antioxidant 300 used in example 1. Polyester composition A9 and nonwoven B9 were obtained.
Example 10
This example is for illustrating the heat shrinkable film and the method of manufacturing the same provided by the present invention.
The procedure is as in example 1, except that 0.25kg of antioxidant 300 is not added. Polyester composition A10 and heat-shrinkable film B10 were obtained.
Comparative example 1
The procedure of example 1 was followed except that the polyester A of example 1 was directly prepared into a non-woven fabric DB1 without the blending process with the polyester B of example 1.
Comparative example 2
The procedure of example 1 was followed except that the polyester B of example 1 was directly prepared into a non-woven fabric DB2 without the blending process with the polyester A of example 1.
Comparative example 3
Nonwoven DB3 was prepared according to the method of example 1, except that the same weight of polybutylene terephthalate (available from DuPont under the trademark Crastin SC164NC010, the same applies below) was used in place of the polyester A used in example 1.
Comparative example 4
Nonwoven fabric DB4 was prepared by following the procedure of example 1, except that the same weight of polybutylene terephthalate was used in place of polyester B used in example 1.
Comparative example 5
Nonwoven fabric DB5 was prepared by following the procedure of example 1, except that the same weight of polybutylene succinate (available from BASF corporation under the designation 1111HTA4, the same applies hereinafter) was used in place of the polyester A used in example 1.
Comparative example 6
Nonwoven fabric DB6 was prepared by following the procedure of example 1, except that the same weight of polybutylene succinate was used in place of polyester B used in example 1.
Comparative example 7
The procedure of example 1 was followed, except that the amount of polyester A was 2kg and the amount of polyester B was 3kg, to obtain nonwoven DB 7.
Comparative example 8
The procedure is as in example 1, except that 2.5kg of polyester A and 2.5kg of polyester B are used, giving DB8 film.
Comparative example 9
The procedure is as in example 1, except that polybutylene terephthalate is directly prepared into the nonwoven DB 9.
Comparative example 10
The procedure of example 1 was followed, except that polybutylene succinate was directly used as a nonwoven fabric DB 10.
Test examples 1 to 20
The water absorption test adopts two methods to verify, namely a non-woven fabric dripping test and a material contact angle test to water. The specific test procedure is as follows.
Water dropping experiment: dropping a drop of deionized water on the surface of the prepared non-woven fabric by using a dropper, and marking the result as 'seeping' if the drop of the deionized water freely permeates through the non-woven fabric; if the water droplet floats on the surface and maintains a good shape, similar to the existing shape of a water droplet on the surface of a lotus leaf, the result is marked as a "droplet".
Contact angle test: the composition obtained in each of the examples or comparative examples was pressed into a 70 mm. times.70 mm. times.1 mm sheet at 170 ℃ under a pressure of 4000 kgs. Subsequently, a drop of deionized water was carefully placed on the surface of the sheeting with a pipette gun, and then the shape of the drop was photographed laterally with the macro mode of the camera, and the contact angle of the drop with the surface of the material was read from the picture. If the contact angle is less than 90 °, the result is labeled "hydrophilic"; if the contact angle is greater than 90 deg., the result is labeled "hydrophobic".
Air permeability test: a balloon was wrapped around a narrow tube having an inner diameter of about 1mm, and inflated to the same size. The balloon is freely deflated through a thin tube, and the time is t1. A small piece of the nonwoven fabric of the example or comparative example was subsequently covered in the narrow tube opening and the time to empty was measured and recorded as t2. If t is2Less than 2 xt1The result is labeled "breathable" otherwise labeled "non-breathable".
Ethanol resistance test: the ethanol-resistant experiment is used for indicating whether the non-woven fabric reacts with ethanol or is dissolved in the ethanol sterilization process so as to reflect the sterilization easiness of the non-woven fabric. Specifically, 2g of a nonwoven fabric sample was placed in 75 vol% ethanol at room temperature for 24 hours, and then dried in the air, and the surface of the nonwoven fabric sample was observed and weighed. If the sample simultaneously satisfies (1) no apparent change in appearance, (2) a weight not less than 99% of the original weight, the result is marked as "ok", otherwise, it is marked as "no".
Heat shrinkage test: a piece of 10cm × 10cm nonwoven fabric was placed in hot water (80 ℃, 90 ℃, 95 ℃) for 10 seconds, and then taken out, the size thereof was measured, and the percentage of the area of the nonwoven fabric in the reduced portion to the initial area was calculated.
The results of the above drip test, contact angle test, air permeability test, ethanol resistance test and heat shrinkage test are shown in tables 1 and 2.
TABLE 1
| Non-woven fabric | Drip test | Contact Angle test | Air permeability test | Ethanol tolerance test | |
| Test example 1 | B1 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 2 | B2 | Oozing the mixture | Hydrophilic | Is breathable | Can be prepared by |
| Test example 3 | B3 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 4 | B4 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 5 | B5 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 6 | B6 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 7 | B7 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 8 | B8 | Oozing the mixture | Hydrophilic | Is breathable | Can be used for |
| Test example 9 | B9 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 10 | B10 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 11 | DB1a | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 12 | DB2 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 13 | DB3a | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 14 | DB4b | - | - | - | - |
| Test example 15 | DB5a | Oozing out | Hydrophilic | Is breathable | Can be prepared by |
| Test example 16 | DB6a | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 17 | DB7 | Oozing out | Hydrophilic | Air permeability | Can be used for |
| Test example 18 | DB8 | Oozing out | Hydrophilic | Is breathable | Can be used for |
| Test example 19 | DB9b | - | - | - | - |
| Test example 20 | DB10a | Oozing out | Hydrophilic | Is breathable | Can be used for |
Note: "a" indicates that the non-woven fabric formed by processing has low yield and is easy to damage;
"b" indicates that no nonwoven fabric could be obtained;
"-" indicates no measurement.
TABLE 2
Test examples 1 to 20
The non-woven fabrics prepared in examples 1 to 10 and comparative examples 1 to 10 were respectively prepared into disposable gowns, and after clinical use, the discarded disposable gowns were soaked in boiling water for sterilization.
As a result, it was found that the disposable gowns made of the nonwoven fabrics B1-B10 obtained in examples 1 to 10 were greatly shrunk in boiling water, and the volume was remarkably reduced, thereby facilitating the recovery. The recovered material was fed again to a spunbond machine as a raw material for producing a nonwoven fabric, and the nonwoven fabric was produced again under the conditions of the spunbond method in example 1. Meanwhile, the newly produced nonwoven fabrics were found to have similar properties to the nonwoven fabrics B1-B10 produced in the above examples 1-10, and to be suitable for further use as raw materials for disposable medical textile products,
thereby realizing the recycling of materials.
The disposable gowns made of the nonwoven fabrics DB1-DB10 obtained in comparative examples 1 to 10 had little change in volume in boiling water, which made the recycling work troublesome. The recovered material was fed again to the spunbond machine as a raw material for preparing a nonwoven fabric, and a nonwoven fabric was prepared again under the conditions of the spunbond method in example 1. As a result, some of them were found to be unable to be molded well, while others did not have good heat-shrinkable properties and were not suitable for further use as a raw material for disposable medical textile products.
As can be seen from the results of the above test examples 1 to 20 and test examples 1 to 20, the nonwoven fabric obtained by blending specific copolymers (polyester A and polyester B) in a specific compounding ratio (polyester A content of 51 to 99% by weight and polyester B content of 1 to 49% by weight) according to the present invention has good water absorption, air permeability and sterilization, in particular, the nonwoven fabric of the present invention can be sterilized in hot water (e.g., 100 ℃) and greatly shrunk, thus being easily compressed to a small volume, facilitating the recovery and reproduction of materials, in particular disposable materials, moreover, the re-produced non-woven fabric has similar performance to the non-woven fabric used for the first time, and is suitable for being continuously used as a raw material of disposable non-woven fabric products (particularly disposable medical textile products), thereby well solving the problem of recycling the materials.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (27)
1. A polyester composition, characterized in that the polyester composition comprises the following components, based on the total weight of the components:
(1)55 to 70 weight percent of polyester A, the polyester A is a copolymer containing a repeating unit A shown in a formula (I) and a repeating unit B shown in a formula (II), and the content of the repeating unit A is 81 to 95 mol percent and the content of the repeating unit B is 5 to 19 mol percent based on the total mole number of the repeating unit A and the repeating unit B in the polyester A,
wherein m1 is an integer of 2 to 4, n1 is an integer of 2 to 4, m1 and n1 are the same or different, and the weight-average molecular weight of the polyester A is 50,000-900,000;
(2)30 to 45% by weight of a polyester B which is a copolymer comprising a repeating unit C represented by the formula (III) and a repeating unit B represented by the formula (II), wherein the content of the repeating unit C is 40 to 70% by mole and the content of the repeating unit B is 30 to 60% by mole, based on the total number of moles of the repeating unit C and the repeating unit B in the polyester B,
wherein m2 is an integer of 2 to 4, n2 is an integer of 2 to 4, m2 and n2 are the same or different, and the weight-average molecular weight of the polyester B is 50,000-900,000.
2. The polyester composition according to claim 1, wherein in formula (I), m1 is an integer from 2 to 4, and n1 is 2.
3. The polyester composition according to claim 1, wherein the weight average molecular weight of the polyester A is 100,000-500,000.
4. The polyester composition according to claim 1, wherein in formula (II), m2 is an integer from 2 to 4, and n2 is 2.
5. The polyester composition according to claim 1, wherein the weight average molecular weight of the polyester B is 100,000-500,000.
6. The polyester composition of any of claims 1-5, wherein the polyester composition further comprises an auxiliary filler.
7. The polyester composition of claim 6, wherein the auxiliary filler is present in an amount of 0.1 to 25 wt.%, based on the total weight of the polyester composition.
8. The polyester composition of claim 7, wherein the auxiliary filler is present in an amount of 1 to 20 wt.%, based on the total weight of the polyester composition.
9. The polyester composition of claim 6, wherein the auxiliary filler is selected from at least two of calcium carbonate, carbon black, talc, erucamide, titanium dioxide, iron oxide, metal carboxylates, metal phosphates, tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, low density polyethylene, polyphosphates, phosphites, hindered phenols, hindered amines, dibenzylsorbitol and its derivatives, hyperbranched polyamides, and ethylene-methacrylic ionomers.
10. The polyester composition of claim 9, wherein the auxiliary filler is selected from at least two of calcium carbonate, carbon black, erucamide, titanium dioxide, tris (2, 3-dibromopropyl) phosphate, low density polyethylene, and hyperbranched polyamides.
11. A process for the preparation of a polyester composition according to any of claims 1 to 10, characterized in that it comprises: polyester A and polyester B are blended, and the resulting mixture is subjected to extrusion granulation.
12. The production method according to claim 11, wherein the blending is performed in the presence of an auxiliary filler.
13. The method of claim 11, wherein the auxiliary filler is present in an amount of 0.1 to 25 wt%, based on the total weight of the polyester composition.
14. The method of claim 13, wherein the auxiliary filler is present in an amount of 1 to 20 wt%, based on the total weight of the polyester composition.
15. The method of claim 11, wherein the blending is performed without the addition of a compatibilizer.
16. The method as claimed in claim 11, wherein the temperature of the extrusion granulation is 140-220 ℃.
17. The method as claimed in claim 16, wherein the temperature of the extrusion granulation is 160-200 ℃.
18. A nonwoven fabric comprising the polyester composition according to any one of claims 1 to 10 and/or the polyester composition obtained by the production method according to any one of claims 11 to 17.
19. A method for preparing a nonwoven fabric, the method comprising: a nonwoven fabric obtained by a spunbonding method using the polyester composition according to any one of claims 1 to 10 and/or the polyester composition obtained by the production method according to any one of claims 11 to 17.
20. The method of claim 19, wherein the spunbonding process comprises extrusion, spinning, netting, and consolidation processes.
21. The method as claimed in claim 20, wherein the extrusion process comprises three temperature zones, the first temperature zone is at a temperature of 140-.
22. The preparation method as claimed in claim 20, wherein the spinning temperature is 150-240 ℃ and the spinning speed is 10-40 r/min.
23. The method of claim 20, wherein the web formation rate is 5 to 30 r/min.
24. The method of claim 20, wherein the consolidation is performed by hot rolling at a temperature of 80-170 ℃.
25. Use of the polyester composition according to any one of claims 1 to 10, of the polyester composition obtained by the process according to any one of claims 11 to 17, of the nonwoven fabric according to claim 18, of the nonwoven fabric obtained by the process according to any one of claims 19 to 24 in nonwoven fabric articles.
26. The use of claim 25, wherein the nonwoven article is a disposable nonwoven article.
27. The use of claim 26, wherein the nonwoven article is a disposable medical nonwoven article.
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| CN201710703774.4A CN109401215B (en) | 2017-08-16 | 2017-08-16 | Polyester composition and non-woven fabric, and preparation method and application thereof |
| JP2019520899A JP2020502288A (en) | 2016-10-21 | 2017-10-20 | Polyester composition, its production method and its application |
| EP17862862.4A EP3530694A4 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| PCT/CN2017/107106 WO2018072746A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| US16/343,711 US11466151B2 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
| CA3040988A CA3040988A1 (en) | 2016-10-21 | 2017-10-20 | Polyester composition, preparation method therefor and application thereof |
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