CN112501714A - Ultraviolet absorption PETG material and application thereof - Google Patents

Ultraviolet absorption PETG material and application thereof Download PDF

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Publication number
CN112501714A
CN112501714A CN202011168954.5A CN202011168954A CN112501714A CN 112501714 A CN112501714 A CN 112501714A CN 202011168954 A CN202011168954 A CN 202011168954A CN 112501714 A CN112501714 A CN 112501714A
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Prior art keywords
petg
fiber
ultraviolet absorption
skin
core
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王翔宇
欧雪光
孔林明
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Yinjinda Shanghai New Material Co ltd
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Yinjinda Shanghai New Material Co ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses an ultraviolet absorption PETG material, which is a PETG fiber with a skin-core structure. Can be added into various polymer materials to achieve the effect of ultraviolet absorption. Finally, the glass can be used for the application of outer wall glass, window films, glasses films and the like. Has the advantages of lasting function and no migration.

Description

Ultraviolet absorption PETG material and application thereof
Technical Field
The invention relates to a PETG material, in particular to an ultraviolet absorption PETG fiber.
Background
Ultraviolet rays can cause harm to human health, partial wavelengths of ultraviolet rays can penetrate through skin, therefore, the ultraviolet rays need to be shielded, and chemical bonds of most materials can be damaged under the irradiation of the ultraviolet rays, so that the service life is seriously influenced.
Because the PETG has excellent performance and is widely applied to various industries, the service life of the PETG is seriously influenced by ultraviolet rays, so the PETG needs to be protected by the ultraviolet rays,
the existing proposal is to add ultraviolet absorbent, the existing ultraviolet absorbent can migrate out of the system, and most of the ultraviolet absorbent can cause more harm to human bodies if directly contacting human bodies, for example, the ultraviolet absorbent Tinuvin770 can cause rats to have cardiotoxicity.
Therefore, the problem that the ultraviolet absorbent in the ultraviolet absorption PETG material migrates to the surface in the PETG material and is harmful to human bodies needs to be solved.
Disclosure of Invention
In order to solve the problems that an ultraviolet absorbent in an ultraviolet absorbing material in the current market migrates to the surface in a PETG material and can harm human bodies, the invention discloses an ultraviolet absorbing PETG fiber which can be added into polyester materials such as PET or PETG and the like to play a role of ultraviolet absorption, can be finally used for outer wall glass, vehicle window films or glasses films and the like, has the advantage of lasting function and is not subjected to migration.
The ultraviolet absorption PETG material is a skin-core structure fiber, wherein the skin layer is made of a common PETG material, and the core layer is made of an ultraviolet absorption PETG material.
As a further scheme of the invention, the core-sheath structure fiber used in the invention has a core layer thickness diameter of 20-30um and a sheath layer thickness sum of 5-15 um.
As a further aspect of the present invention, the uv-absorbing core material used in the present invention is a uv-absorbing material grafted PETG polymer, more particularly a terminal graft material, which can be uniformly dispersed in the fiber core layer due to its terminal graft property.
As a further scheme of the invention, the structural general formula of the core layer ultraviolet absorption material composite PETG polymer used by the invention is as follows:
Figure RE-GDA0002932200700000021
wherein n: m is 8:2-6:4, n + m is 30-100.
As a further scheme of the invention, the core layer ultraviolet absorbing material composite PETG polymer used by the invention can absorb ultraviolet rays under the irradiation of the ultraviolet rays.
As a further aspect of the present invention, the core layer uv-absorbing material used in the present invention can turn blue under uv irradiation and then turn colorless under a dark environment, and the mechanism of the color change is as follows:
Figure RE-GDA0002932200700000022
as a further scheme of the invention, the ultraviolet absorption material of the core layer used in the invention can better shield ultraviolet rays after discoloration.
As a further scheme of the invention, the preparation method of the ultraviolet absorption composite PETG general structural formula used in the invention comprises the following steps:
Figure RE-GDA0002932200700000023
Figure RE-GDA0002932200700000031
as a further aspect of the present invention, the sheath-core structure PET fiber used in the present invention has an outer layer material obtained by copolymerizing terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol.
As a further scheme of the invention, the preparation method of the PET fiber with the sheath-core structure used in the invention is bicomponent fiber spinning.
As a further scheme of the invention, the preparation method of the sheath-core structure PET fiber used in the invention comprises the steps of respectively crystallizing and drying two components, extruding the two components through screws, wherein the core layer extrusion temperature is 280 plus materials and the skin layer extrusion temperature is 250 plus materials and 280 ℃, spinning is carried out through composite spinning equipment, and the two components are wound through winding equipment after the spinning is finished.
The technical scheme provided by the invention has the beneficial effects that:
the self-made ultraviolet absorption material can be changed into blue under strong ultraviolet, better blocks ultraviolet and can be changed into colorless under normal light.
By grafting the uv-absorbing material onto the polymer, the uv-absorbing material can be uniformly dispersed in the fiber core layer due to the grafting at the end thereof.
By grafting the uv absorbing material onto the polymer, its durability is improved.
By preparing the fiber in a sheath-core structure, the ultraviolet absorbing material is effectively prevented from migrating outwards.
Detailed description of the invention
The present invention will be further described below by way of specific examples.
In the following specific examples, those whose operations are not subject to the conditions indicated are carried out according to conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the scheme of the invention are purchased from Chinese medicines and Aladdin.
Preparation of ultraviolet absorption functional end group:
carrying out sodium iodide catalytic reaction on 0.1mol of 1,1, 2-trimethyl-1H-benzindole and 0.2mol of bromoethane under anhydrous and oxygen-free conditions for 8 hours, then recrystallizing by using n-hexane and ethyl acetate, adding a recrystallization product into a sodium hydroxide aqueous solution for hydrolysis, and obtaining an intermediate 1 after complete hydrolysis with a yield of 41.5%;
0.1mol of the intermediate 1 and 0.13mol of 3-formyl-4-hydroxybenzoic acid are reacted for 24 hours at the temperature of 60 ℃ under the catalysis of triethylamine, and ultraviolet absorption functional end groups are obtained by passing through a column, and the yield is 85.4%.
Preparing a skin layer material:
adding 1mol of terephthalic acid, 0.4mol of ethylene glycol and 0.6mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 250 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, vacuumizing, removing generated water, adding an antimony acetate catalyst with the total mass of 0.5% when no water is distilled out from a reflux pipeline, heating to 280 ℃, continuously carrying out vacuum polycondensation reaction until the feedback value of the stirring power reaches a set value, and discharging.
Example 1
Adding 0.1mol of ultraviolet absorption functional material end group, 1.4mol of terephthalic acid, 1.2mol of ethylene glycol and 0.3mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 250 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.5% when no water is distilled out from a reflux pipeline, starting to heat to 280 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
respectively feeding 650g of the skin layer material and 314g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 300 ℃, the skin layer extrusion temperature is 250 ℃, spinning by composite spinning equipment, and winding by winding equipment after spinning.
Example 2
Adding 0.1mol of ultraviolet absorption functional material end group, 2.9mol of terephthalic acid, 2.1mol of ethylene glycol and 0.9mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 260 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.3 percent when no water is distilled out from a reflux pipeline, starting to heat to 280 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
and respectively feeding 471g of the skin layer material and 490g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 290 ℃, the skin layer extrusion temperature is 260 ℃, spinning is carried out through composite spinning equipment, and the spinning is wound through winding equipment after the spinning is finished.
Example 3
Adding 0.1mol of ultraviolet absorption functional material end group and 1.9mol of terephthalic acid, 1.2mol of ethylene glycol and 0.8mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 270 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.2% when no water is distilled out from a reflux pipeline, starting to heat to 280 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
and respectively feeding 442g of the skin layer material and 355g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 280 ℃, the skin layer extrusion temperature is 250 ℃, spinning is carried out through composite spinning equipment, and the spun yarn is wound through winding equipment after being spun.
Example 4
Adding 0.1mol of ultraviolet absorption functional material end group, 2.4mol of terephthalic acid, 2.0mol of ethylene glycol and 0.5mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 270 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.2% when no water is distilled out from a reflux pipeline, starting to heat to 280 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
and (3) respectively feeding 176g of the skin layer material and 314g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 300 ℃, the skin layer extrusion temperature is 250 ℃, spinning is carried out through composite spinning equipment, and the spinning is wound through winding equipment after the spinning is finished.
Example 5
Adding 0.1mol of ultraviolet absorption functional material end group, 3.9mol of terephthalic acid, 2.8mol of ethylene glycol and 1.2mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 270 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.3% when no water is distilled out from a reflux pipeline, starting to heat to 290 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
and respectively feeding 335g of the skin layer material and 572g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 290 ℃, the skin layer extrusion temperature is 250 ℃, spinning is carried out through composite spinning equipment, and the spinning is wound through winding equipment after the spinning is finished.
Example 6
Adding 0.1mol of ultraviolet absorption functional material end group, 3.4mol of terephthalic acid, 2.8mol of ethylene glycol and 0.7mol of 1, 4-cyclohexanedimethanol into a reactor, slowly heating to 270 ℃ under the pressure of 0.5mpa, continuously reacting for 6 hours, removing the pressure of 0.5mpa, starting to vacuumize, removing generated water, adding an antimony acetate catalyst with the total mass of 0.5% when no water is distilled out from a reflux pipeline, starting to heat to 280 ℃, continuously carrying out vacuum polycondensation reaction until the stirring power feedback value reaches a set value, and discharging;
and (3) respectively feeding 527g of the skin layer material and 379g of the ultraviolet absorbing group modified PETG resin into a melting furnace, wherein the core layer extrusion temperature is 290 ℃, the skin layer extrusion temperature is 250 ℃, spinning is carried out through composite spinning equipment, and the spun materials are wound through winding equipment after spinning is finished.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, as any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention mainly relates to an ultraviolet absorption PETG material which is a PETG fiber with a skin-core structure, can permanently absorb ultraviolet light, can turn blue under strong light and can restore to be colorless under dark light, so that the fiber size, the ultraviolet absorption intensity and the ultraviolet aging resistance of the PETG fiber are tested by using a microscope.
Fiber size:
the fiber yarn is fixed on a glass slide, a layer of high-purity dimethyl silicone oil is covered on the surface, and the fiber yarn is observed by using a Saimer Fei EVOS M5000 type optical microscope, wherein the multiple is 200 times.
The fiber size was tested using an optical microscope.
Figure RE-GDA0002932200700000061
Figure RE-GDA0002932200700000071
. Ultraviolet absorption intensity:
examples 1-6 were dispersed in DMF at a concentration of 0.1g/L, scanned over a 200-400nm wavelength band on an ultraviolet spectrophotometer, and the absorption coefficients recorded.
Examples 1-6 were placed in the sun for 30 days, likewise dispersed in DMF at a concentration of 0.1g/L, scanned over a wavelength band of 200-400nm on a UV spectrophotometer and the molar absorption coefficient was recorded.
Absorption coefficient Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Day 0 13122 13505 9870 28790 18349 17933
30 days 13011 12403 9785 27015 17994 17731
. As can be seen from the above table, examples 1 to 6 of the present invention all had good UV absorption effect, and the absorption intensity did not significantly decrease after 30 days, and had good long-term performance.

Claims (9)

1. The invention relates to an ultraviolet absorption PETG material, which is a PETG fiber with a skin-core structure, wherein the skin layer is a common PETG material, and the core layer is an ultraviolet absorption PETG material.
2. The method as claimed in claim 1, wherein the core layer UV-absorbing PETG material used in the present invention is UV-absorbing material-grafted PETG polymer.
3. The fiber of claim 1, wherein the core layer has a diameter of 20-30um and the sum of the thicknesses of the skin layers is 5-15 um.
4. The ultraviolet absorbing material of the core layer grafted PETG structure according to the invention as claimed in claim 2, has the general formula:
Figure RE-FDA0002932200690000011
wherein n: m is 8:2-6:4, n + m is 30-100.
5. The method for preparing the core layer ultraviolet absorption grafted PETG with the structural general formula as shown in claim 4 is characterized by comprising the following steps:
(1)
Figure RE-FDA0002932200690000012
(2)
Figure RE-FDA0002932200690000013
(3)
Figure RE-FDA0002932200690000014
Figure RE-FDA0002932200690000021
6. the PETG fiber of the sheath-core structure according to claim 1, wherein the outer layer material of the PETG fiber of the sheath-core structure is composed of terephthalic acid, ethylene glycol and 1, 4-cyclohexanedimethanol.
7. The method of claim 1, wherein the core-sheath PET fiber is prepared by bicomponent fiber spinning.
8. The method for preparing the PETG fiber with the skin-core structure according to claim 1 comprises the steps of respectively crystallizing and drying two components, respectively extruding the two components through a screw, wherein the core layer extrusion temperature is 280-300 ℃, the skin layer extrusion temperature is 250-280 ℃, spinning is carried out through composite spinning equipment, and the fibers are wound through winding equipment after the spinning is finished.
9. The ultraviolet absorption PETG material of claim 1 is PETG fiber with a skin-core structure, can be added into various polymer materials to achieve an ultraviolet absorption effect, can be used for application of outer wall glass, vehicle window films or glasses films and the like by adding the polymer material, and has the advantages of lasting ultraviolet absorption function and no migration.
CN202011168954.5A 2020-10-28 2020-10-28 Ultraviolet absorption PETG material and application thereof Withdrawn CN112501714A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116862A (en) * 1976-04-30 1978-09-26 Essilor International (Compagnie Generale D'optique) New photochromic materials and method for their preparation
CN1182114A (en) * 1997-11-12 1998-05-20 南开大学戈德防伪技术公司 Photochromic spiro-compound and its preparation
JPH11158735A (en) * 1997-11-28 1999-06-15 Seiren Co Ltd Sheath core type conjugated fiber having improved light resistance and production of the same
EP1471110A1 (en) * 2003-04-23 2004-10-27 Nan Ya Plastics Corporation Polyester composition reducing ultraviolet light penetration and a polyester bottle manufactured from said polyester composition
CN105482085A (en) * 2015-11-24 2016-04-13 清华大学 Anti-ultraviolet copolyester and preparation method thereof
CN108148576A (en) * 2018-03-05 2018-06-12 天津孚信阳光科技有限公司 A kind of coloured bleach photochromic compound and preparation method thereof
CN109402780A (en) * 2017-11-30 2019-03-01 天津孚信阳光科技有限公司 Photochromic composite fibre

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4116862A (en) * 1976-04-30 1978-09-26 Essilor International (Compagnie Generale D'optique) New photochromic materials and method for their preparation
CN1182114A (en) * 1997-11-12 1998-05-20 南开大学戈德防伪技术公司 Photochromic spiro-compound and its preparation
JPH11158735A (en) * 1997-11-28 1999-06-15 Seiren Co Ltd Sheath core type conjugated fiber having improved light resistance and production of the same
EP1471110A1 (en) * 2003-04-23 2004-10-27 Nan Ya Plastics Corporation Polyester composition reducing ultraviolet light penetration and a polyester bottle manufactured from said polyester composition
CN105482085A (en) * 2015-11-24 2016-04-13 清华大学 Anti-ultraviolet copolyester and preparation method thereof
CN109402780A (en) * 2017-11-30 2019-03-01 天津孚信阳光科技有限公司 Photochromic composite fibre
CN108148576A (en) * 2018-03-05 2018-06-12 天津孚信阳光科技有限公司 A kind of coloured bleach photochromic compound and preparation method thereof

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