CN110172182B - Special polyester tackifying/nucleating aid, preparation thereof and application thereof in PET modification - Google Patents
Special polyester tackifying/nucleating aid, preparation thereof and application thereof in PET modification Download PDFInfo
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- CN110172182B CN110172182B CN201910324490.3A CN201910324490A CN110172182B CN 110172182 B CN110172182 B CN 110172182B CN 201910324490 A CN201910324490 A CN 201910324490A CN 110172182 B CN110172182 B CN 110172182B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention discloses a special polyester tackifying/nucleating aid, a preparation method thereof and application thereof in PET modification. The special polyester tackifying/nucleating additive is an inorganic nonmetallic particle which is obtained by carrying out surface modification on an inorganic nonmetallic particle by using a silane coupling agent and contains a functional group and short-chain alkyl on the surface; the silane coupling agent consists of at least one silane coupling agent with a functional group at the tail end and at least one silane coupling agent with a short chain alkyl at the tail end, wherein the functional group is a group capable of reacting with-OH or-COOH at the end of a polyester molecule chain, and the number of carbon atoms of the short chain alkyl is 3-8; the surface of the inorganic nonmetallic particle contains hydroxyl or carboxyl, and the particle size range of the inorganic nonmetallic particle is 10-200 nm. The auxiliary agent provided by the invention can realize polyester tackifying and crystallization nucleation induction at the same time. The invention also provides a PET modification method which is simple and low in cost and can simultaneously realize PET tackifying and crystallization nucleation induction.
Description
(I) technical field
The invention relates to a special polyester tackifying/nucleating aid, a preparation method thereof and application thereof in modification of polyethylene terephthalate (PET).
(II) background of the invention
PET is a cheap and excellent-performance general engineering plastic, and particularly PET waste is extremely abundant in society along with the increasing expansion of beverage consumption markets, so that the PET waste is in urgent need of recycling. However, the molecular chain of PET is often broken during extrusion and injection molding, and particularly after the PET is exposed to the sun and rain, the molecular weight of the PET is obviously reduced, and the mechanical property of the PET is obviously reduced. For reuse, especially industrial reuse (not for general use), it is necessary to increase the molecular weight, i.e., to extend the chain and increase the viscosity.
On the other hand, although PET is inexpensive, it has a long injection molding cycle due to its low crystallization rate, and is rarely used for injection molding other than a bottle preform. In order to shorten the injection molding cycle, improve the production efficiency and improve the mechanical and heat-resistant properties, the melt crystallization rate must be increased. The addition of a crystallization nucleating agent is a good method for increasing the crystallization rate, and inorganic non-metallic nanoparticles are the most commonly used crystallization nucleating agents.
The PET chain extension tackifier commonly used in the market at present is an oligomer containing an active epoxy group, and the tackifying principle is that PET chain extension is realized by the reaction of the epoxy group and PET macromolecular chain end-COOH during blending. The commonly used crystal nucleating agent for PET at present comprises inorganic and organic substances, wherein the inorganic substance is mainly nano-particles, such as CaCO3、SiO2And TiO2And the like.
However, the existing chain extender and the existing crystallization nucleating agent are respectively 'chemical', and if the chain extender and the crystallization nucleating agent can be unified, namely one material can be used for chain extension and can induce crystallization nucleation, the application value is higher.
Disclosure of the invention
The invention aims to provide a special additive for polyester tackifying/nucleating, which can realize polyester tackifying and crystallization-induced nucleation simultaneously.
The second purpose of the invention is to provide a preparation method of the special polyester tackifying/nucleating additive.
The third purpose of the invention is to provide a simple and low-cost PET modification method which can simultaneously realize PET tackifying and crystallization nucleation induction.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
on one hand, the invention provides a special assistant for polyester tackifying/nucleating, which is an inorganic nonmetallic particle with a functional group and short-chain alkyl on the surface, and is obtained by surface modification of the inorganic nonmetallic particle by a silane coupling agent; the silane coupling agent consists of at least one silane coupling agent with a functional group at the tail end and at least one silane coupling agent with a short chain alkyl at the tail end, wherein the functional group is a group capable of reacting with-OH or-COOH at the end of a polyester molecule chain, and the number of carbon atoms of the short chain alkyl is 3-8; the surface of the inorganic non-metal particle contains hydroxyl or carboxyl, and the particle size range of the inorganic non-metal particle is 10-200 nm; the mass ratio of the silane coupling agent to the inorganic nonmetal particles is 1-10: 100, the molar ratio of the silane coupling agent containing the functional group at the end is 20-80%, preferably 30-70%.
Preferably, the mass ratio of the silane coupling agent to the inorganic nonmetallic particles is 2 to 8: 100, more preferably 3 to 5: 100.
the inorganic non-metal particles of the invention are preferably SiO with hydroxyl on the surface2、TiO2、CaCO3ZnO, clay or graphene oxide. In the invention, the higher the hydroxyl content on the surface of the inorganic nonmetallic particle is, the better the modification and tackifying effects are.
The silane coupling agent used for surface modification of the inorganic nonmetallic particles consists of at least one silane coupling agent with the tail end containing a functional group and at least one silane coupling agent with the tail end containing short-chain alkyl, wherein the silane coupling agent can realize the reaction of the inorganic nonmetallic particles and the polyester molecular chain end groups, and the silane coupling agent can improve the compatibility between the inorganic nonmetallic particles and PET to ensure that the particles are uniformly and nano-dispersed in the PET. Preferably, the functional group may be a carboxyl group (-COOH), an epoxy group or an amine group (-NH)2). The silane coupling agent with the terminal functional group is preferably KH550 or KH 560. The silane coupling agent with the short-chain alkyl at the tail end is preferably n-hexyltriethoxysilane or n-octyltriethoxysilane.
In a second aspect, the invention provides a preparation method of the special polyester tackifying/nucleating agent, which comprises the following steps:
(a) uniformly mixing an ethanol/water mixed solution, a silane coupling agent and inorganic non-metal particles under stirring, then adjusting the pH value to 3.5-4.5 by using hydrochloric acid (preferably dilute hydrochloric acid, such as dilute hydrochloric acid with the concentration of about 10 wt%), fully mixing at room temperature, hydrolyzing the silane coupling agent under the weak acid condition to obtain silanol containing silicon hydroxyl, and coating the inorganic non-metal particles by the hydrolyzed silane coupling agent containing functional groups to obtain stable slurry with the solid content of 5-20 wt%; the feeding mass ratio of the silane coupling agent to the inorganic nonmetal particles is 1-10: 100, the silane coupling agent consists of at least one silane coupling agent with a functional group at the tail end and at least one silane coupling agent with a short-chain alkyl at the tail end, and the silane coupling agent with the functional group at the tail end accounts for 20-80% of the silane coupling agent;
(b) centrifuging and drying the slurry obtained in the step (a) to obtain inorganic nonmetal nanoparticles with the surface containing functional groups and short chain alkyl, namely the special polyester tackifying/nucleating aid.
In the step (a), after the pH is adjusted to 3.5-4.5, solid and liquid need to be fully mixed to obtain stable slurry, and the mixing mode may be one or a combination of several of stirring, ultrasonic, ball milling and the like. Preferably, the mixing method comprises ball milling, and the inorganic non-metal particles can be nanocrystallized and coated by the hydrolyzed silane coupling agent containing the functional group through the ball milling, so that the performance of the auxiliary agent is further improved. The ball milling conditions recommended by the invention are as follows: the diameter of the zirconium beads is 0.2-1mm, the dispersion liquid with the mass of 50-400g/3000mL is added into the zirconium beads, the rotating speed is 300-450rpm, and the ball milling time is 3-8h, so that the stable slurry is obtained.
Preferably, the ethanol/water mixture in step (a) has a volume ratio of ethanol of 20-40%.
Preferably, in the step (a), the charging mass ratio of the silane coupling agent to the inorganic nonmetal particles is 2-8: 100, more preferably 3 to 5: 100.
preferably, in step (b), the drying is oven drying or spray drying. Further preferred oven drying conditions are: drying with air blast at 60-80 deg.C for 12-15 hr. Further preferably, the spray drying conditions are 190 ℃ and the slurry inlet rate is 5 mL/min.
In a third aspect, the invention provides a modification method of PET, which is implemented according to the following steps: the special additive for polyester tackifying/nucleating is added into PET, so that the additive is uniformly dispersed in the PET, and functional groups contained on the surface of the additive react with-OH or-COOH at the molecular chain end of the PET to obtain modified PET, namely the PET is tackified and crystallized to induce nucleating.
The PET of the invention can be PET basic slices, PET return materials obtained by crushing and washing PET waste films, sheets, threads or PET waste bottles, or PET machine head materials.
The invention preferably realizes the uniform dispersion of the inorganic non-metal particles in the PET and the reaction of the functional groups contained on the surfaces of the inorganic non-metal particles and-OH or-COOH at the molecular chain ends of the PET by the following modes: the mixture of the special polyester tackifying/nucleating aid and the PET is sent into an internal mixer or a twin-screw extruder and is internally mixed or extruded at the temperature of 230 ℃ and 280 ℃ (preferably at the temperature of 240 ℃ and 270 ℃) to obtain the modified PET.
In the invention, the dosage of the special polyester tackifying/nucleating additive is 1 to 3 weight percent of the dosage of PET.
The thickening in the present invention means to increase the intrinsic viscosity, i.e., molecular weight, of the polyester.
The crystallization-induced nucleation according to the present invention means increasing the crystallization rate and crystallinity of the polyester.
Compared with the prior art, the invention has the beneficial effects that:
(1) the special polyester tackifying/nucleating additive provided by the invention can realize polyester tackifying and induced crystallization nucleating at the same time, and has the characteristics of high efficiency and high added value.
(2) The preparation method of the special polyester tackifying/nucleating agent provided by the invention is simple and low in cost.
(3) The PET modification method provided by the invention is simple, efficient and low in cost, and not only can realize the tackifying of PET but also can realize crystallization induced nucleation by a one-step method; not only can improve the mechanical property and the heat resistance of the PET, but also can improve the forming processing property of the PET.
Description of the drawings
FIG. 1 is a schematic structural diagram of inorganic non-metallic nanoparticles after surface modification by a silane coupling agent containing epoxy groups at the terminals;
FIG. 2 is a schematic structural diagram of PET modified by inorganic nonmetallic particles with epoxy groups on the surface.
(IV) detailed description of the preferred embodiments
The technical solution of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely illustrative of some, but not all, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
adding 240mL of deionized water, 60mL of industrial alcohol and 30g of SiO2(Vancine New materials Co., Ltd., VK-SP30), 0.261g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) (Allandine Shanghai Biochemical Co., Ltd.), 0.710g of n-octyltriethoxysilane (KH-832) (Allandine Shanghai Biochemical Co., Ltd.) (mol ratio of two siloxanes is 3:7), mixing uniformly under mechanical stirring, adjusting pH to 4 with 10 wt% diluted hydrochloric acid, and stirring at room temperature for 6h to obtain nano-slurry with 10 wt% of solid content. The obtained nano slurry was centrifuged (10000rpm, desk type high speed centrifuge, H/T16MM, Hunan Hexi apparatus and Equipment Co., Ltd.), and the precipitate obtained by the centrifugation was dried in a forced air oven at 80 ℃ for 12 hours to obtain modified nano SiO2And (3) granules.
The obtained modified nano SiO2Adding the particles into PET (pure water bottle material of Wahaha), wherein the adding amount is 1 wt% of the using amount of the PET, uniformly mixing, adding into a torque rheometer (RM-200A, Harbin Hapu electric Co., Ltd.), and banburying at 250 ℃ for 5 min. Modified PET in which nanoparticles were uniformly dispersed was obtained, and the thickening effect was measured by Ubbelohde viscometer (GB/T1632-93, solvent: phenol/tetrachloroethane: 1/1, mass ratio), and the crystallization-inducing effect was measured by DSC. The results show that: the PET characteristic viscosity number is increased from 0.45 to 0.93, and the tackifying effect is obvious. The crystallinity increased from 34.7% to 36.2%.
Comparative example 1:
otherwise, the same as example 1, but changing the dosage of KH-560 from 0.261g to 0.87g, but not adding KH-832, modified nano SiO was obtained2And modifying PET, and measuring tackifying and induced crystallization effects. The results show that: the PET characteristic viscosity number is increased from 0.45 to 0.65, and the thickening effect is certain,but not so much. The crystallinity increased from 34.7% to 35.4%.
Comparative example 2:
the rest is the same as example 1, but the silane coupling agent is not adopted to modify the nano SiO2Obtaining the modified PET, and measuring the tackifying and induced crystallization effects. The results show that: the intrinsic viscosity of PET increased from 0.45 to 0.53 with little tackifying effect. The crystallinity increased from 34.7% to 36.1%.
Example 2:
the rest is the same as example 1, but the modified nano SiO2The addition amount of the particles in the PET is changed to 2 wt%, so that the modified PET is obtained, and the tackifying and induced crystallization effects are measured. The results show that: the PET characteristic viscosity number is increased from 0.45 to 0.96, and the tackifying effect is obvious. The crystallinity increased from 34.7% to 37.7%.
Comparative example 3:
the rest is the same as the comparative example 1, but the nano SiO is modified2The addition amount of the particles in the PET is changed to 2 wt%, so that the modified PET is obtained, and the tackifying and induced crystallization effects are measured. The results show that: the increase in the intrinsic viscosity of PET from 0.45 to 0.79 had a tackifying effect, but not as well as the modification with the addition of KH-832. The crystallinity increased from 34.7% to 37.4%.
Comparative example 4:
the rest is the same as the comparative example 2, but the unmodified nano SiO2The addition amount of the particles in the PET is changed to 2 wt%, so that the modified PET is obtained, and the tackifying and induced crystallization effects are measured. The results show that: the PET intrinsic viscosity is increased from 0.45 to 0.50, and no tackifying effect is achieved. The crystallinity increased from 34.7% to 37.2%.
Comparative example 5:
otherwise, the same as example 1, except that the hydrophilic nano SiO2(Vancine New materials Co., Ltd., VK-SP30) to hydrophobic Nano SiO2(Evonik Industries AG, R812s, average particle size 20-30nm) to obtain modified PET, and measuring the tackifying and crystallization inducing effects. The results show that: the characteristic viscosity number of PET is increased from 0.45 to 0.46, and no tackifying effect is achieved because of the nano SiO with hydrophobic surface2It is difficult to modify the epoxy group. The crystallinity increased from 34.7% to 35.5%.
Example 3:
other embodiments are the same as the embodiments1, but the method for preparing the nano slurry is changed to: pouring the slurry of which the pH value is adjusted by dilute hydrochloric acid into a planetary ball mill (QM-3 SP2, Nanjing university instruments factory) for ball milling, wherein the ball milling conditions are as follows: zirconium beads with diameter of 0.5mm, mass of 350g, rotation speed of 350rpm, ball milling time of 5h to obtain nanometer slurry, and spray drying (190 deg.C, slurry inlet speed of 5mL/min) to obtain modified nanometer SiO2And (3) after the granules are melted and mixed with PET, measuring the tackifying and crystallization inducing effects of the PET. The results show that: the PET characteristic viscosity number is increased from 0.45 to 0.98, and the tackifying effect is obvious. The crystallinity increased from 34.7% to 37.2%.
Example 4:
otherwise, the same procedure as in example 1 was repeated, except that the mass of KH560 was 0.434g, and the mass of KH832 was 0.507g (molar ratio of both: 1). The results show that: the PET characteristic viscosity number is increased from 0.45 to 1.12, the tackifying effect is more obvious, and the tackifying effect is probably related to the improvement of the epoxy group modification ratio. The crystallinity increased from 34.7% to 35.9%.
Example 5:
otherwise, the same procedure as in example 1 was repeated, except that the mass of KH560 was 0.607g and that of KH832 was 0.304g (molar ratio of both: 7: 3). The results show that: the PET characteristic viscosity number is increased from 0.45 to 1.21, the tackifying effect is more obvious, and the tackifying effect is probably related to the improvement of the epoxy group modification ratio. The crystallinity increased from 34.7% to 35.6%.
Example 6:
otherwise, the same as example 1, but using nano SiO2By conversion to nano TiO2(Van Jing New materials Co., Ltd., VK-T03). The results show that: the PET characteristic viscosity number is increased from 0.45 to 0.91, the tackifying effect is obvious, and the other characteristics are shown to be nano SiO2And other nanoparticles with epoxy groups modified on the surface can be used for PET chain extension and tackifying. The crystallinity increased from 34.7% to 37.6%.
Claims (11)
1. A PET modification method is characterized by comprising the following steps: the modification method is implemented according to the following steps: adding the special polyester tackifying/nucleating aid into PET, uniformly dispersing the aid in the PET, and reacting functional groups contained on the surface of the aid with-OH or-COOH at the molecular chain end of the PET to obtain modified PET, and simultaneously realizing tackifying and crystallization-induced nucleation of the PET;
the special polyester tackifying/nucleating additive is an inorganic nonmetallic particle which is obtained by carrying out surface modification on an inorganic nonmetallic particle by using a silane coupling agent and contains a functional group and short-chain alkyl on the surface; the silane coupling agent consists of at least one silane coupling agent with a functional group at the tail end and at least one silane coupling agent with a short chain alkyl at the tail end, wherein the functional group is a group capable of reacting with-OH or-COOH at the end of a polyester molecule chain, and the number of carbon atoms of the short chain alkyl is 3-8; the surface of the inorganic non-metal particle contains hydroxyl or carboxyl, and the particle size range of the inorganic non-metal particle is 10-200 nm; the mass ratio of the silane coupling agent to the inorganic nonmetal particles is 1-10: 100, wherein the silane coupling agent with the functional group at the terminal accounts for 20-80% of the total mole ratio.
2. The process for modifying PET according to claim 1, wherein: the uniform dispersion of the inorganic non-metal particles in the PET and the reaction of the functional groups contained on the surfaces of the inorganic non-metal particles and-OH or-COOH at the molecular chain ends of the PET are realized by the following steps: the mixture of the special polyester tackifying/nucleating aid and the PET is sent into an internal mixer or a double-screw extruder to be internally mixed or extruded at the temperature of 230-280 ℃ to obtain the modified PET.
3. A process for the modification of PET as claimed in claim 1 or 2, characterized in that: in the silane coupling agent, the molar ratio of the silane coupling agent with the terminal containing the functional group is 30-70%.
4. A process for the modification of PET as claimed in claim 1 or 2, characterized in that: the inorganic non-metal particles are SiO with hydroxyl on the surface2、TiO2、CaCO3ZnO, clay or graphene oxide.
5. A process for the modification of PET as claimed in claim 1 or 2, characterized in that: the functional group is carboxyl, epoxy or amino.
6. A process for the modification of PET as claimed in claim 1 or 2, characterized in that: the silane coupling agent with the terminal functional group is KH550 or KH 560; the silane coupling agent with the short-chain alkyl at the tail end is n-hexyltriethoxysilane or n-octyltriethoxysilane.
7. A process for the modification of PET as claimed in claim 1 or 2, characterized in that: the special polyester tackifying/nucleating agent is prepared by a preparation method comprising the following steps:
(a) uniformly mixing ethanol/water mixed liquor, a silane coupling agent and inorganic nonmetallic particles under stirring, then adjusting the pH value to 3.5-4.5 by using hydrochloric acid, and fully mixing at room temperature to ensure that the silane coupling agent is hydrolyzed under the weak acid condition to obtain silanol containing silicon hydroxyl and the inorganic nonmetallic particles are coated by the hydrolyzed silane coupling agent containing functional groups to obtain stable slurry with the solid content of 5-20 wt%;
(b) centrifuging and drying the slurry obtained in the step (a) to obtain inorganic nonmetal nanoparticles with the surface containing functional groups and short chain alkyl, namely the special polyester tackifying/nucleating aid.
8. The method of claim 7 for modifying PET, wherein: in the step (a), after the pH is adjusted to 3.5-4.5, the mixing mode at room temperature is one or a combination of more of stirring, ultrasonic and ball milling.
9. The method of claim 7 for modifying PET, wherein: the volume ratio of ethanol in the ethanol/water mixed solution in the step (a) is 20-40%.
10. The method of claim 7 for modifying PET, wherein: in the step (a), the charging mass ratio of the silane coupling agent to the inorganic nonmetal particles is 2-8: 100.
11. the method of claim 7 for modifying PET, wherein: in the step (a), the charging mass ratio of the silane coupling agent to the inorganic nonmetal particles is 3-5: 100.
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| CN110483960A (en) * | 2019-09-17 | 2019-11-22 | 浙江工业大学 | A method of thickening poly terephthalic acid 1,4 cyclohexane dimethanol ester |
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| JPH01278583A (en) * | 1988-05-02 | 1989-11-08 | Fuji Rubber Co Ltd | Printing coating compound composition |
| CN104788925A (en) * | 2015-04-13 | 2015-07-22 | 吴先国 | Compound tackifier for polyester type composite and preparation and application of compound tackifier |
| CN106084215A (en) * | 2016-06-20 | 2016-11-09 | 陕西师范大学 | The bionical method constructing functionalization Janus particle |
| CN106589374A (en) * | 2017-01-04 | 2017-04-26 | 株洲时代新材料科技股份有限公司 | Polyimide thin film and preparation method therefor |
| CN108178986A (en) * | 2017-12-28 | 2018-06-19 | 浙江工业大学 | A kind of calligraphy and painting soil resistant transparent hydrophobic coating and preparation method and application |
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|---|---|---|---|---|
| JPH01278583A (en) * | 1988-05-02 | 1989-11-08 | Fuji Rubber Co Ltd | Printing coating compound composition |
| CN104788925A (en) * | 2015-04-13 | 2015-07-22 | 吴先国 | Compound tackifier for polyester type composite and preparation and application of compound tackifier |
| CN106084215A (en) * | 2016-06-20 | 2016-11-09 | 陕西师范大学 | The bionical method constructing functionalization Janus particle |
| CN106589374A (en) * | 2017-01-04 | 2017-04-26 | 株洲时代新材料科技股份有限公司 | Polyimide thin film and preparation method therefor |
| CN108178986A (en) * | 2017-12-28 | 2018-06-19 | 浙江工业大学 | A kind of calligraphy and painting soil resistant transparent hydrophobic coating and preparation method and application |
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