Amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive and preparation and application thereof
阅读说明：本技术 一种两亲性离聚物增强的健康环保热熔胶及制备与应用 (Amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive and preparation and application thereof ) 是由 李满林 张水洞 张凤帮 童浩瀚 *** 陈君华 胡赞军 于 2020-07-02 设计创作，主要内容包括：本发明属于热熔胶技术领域,公开了一种两亲性离聚物增强的健康环保热熔胶及制备与应用。所述两亲性离聚物增强的健康环保热熔胶包括以下重量份的原料组分：APAO树脂35～45份,SBS树脂5～15份,增粘树脂20～40份,石蜡油10～20份,两亲性聚丁二酸丁二醇酯离聚物5～10份,功能性纳米粒子0～10份。本发明通过在热熔胶中加入两亲性聚丁二酸丁二醇酯离聚物,可显著提升APAO树脂在不同极性表面的浸润性能、提高对非极性表面的粘接性能和固化后的剥离强度。且通过加入功能性纳米粒子,能够赋予热熔胶相应的健康功能及补强性能,提高热熔胶的品质及性能。(The invention belongs to the technical field of hot melt adhesives, and discloses an amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive, and preparation and application thereof. The health environment-friendly hot melt adhesive reinforced by the amphiphilic ionomer comprises the following raw material components in parts by weight: 35-45 parts of APAO resin, 5-15 parts of SBS resin, 20-40 parts of tackifying resin, 10-20 parts of paraffin oil, 5-10 parts of amphiphilic polybutylene succinate ionomer and 0-10 parts of functional nanoparticles. According to the invention, the amphiphilic polybutylene succinate ionomer is added into the hot melt adhesive, so that the wettability of the APAO resin on different polar surfaces can be obviously improved, the adhesion property on the non-polar surfaces and the peel strength after curing are improved. And by adding the functional nano particles, the corresponding health function and reinforcement performance of the hot melt adhesive can be endowed, and the quality and performance of the hot melt adhesive are improved.)
1. An amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive is characterized by comprising the following raw material components in parts by weight:
2. the amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive according to claim 1, characterized in that: the tackifying resin is at least one of rosin resin, terpene resin and terpene phenolic resin.
3. The healthy and environment-friendly hot melt adhesive as claimed in claim 1, wherein: the ionic monomer in the amphiphilic polybutylene succinate ionomer is a phosphorus-containing ionic monomer, the ionic molar concentration is 1-10%, and the number average molecular weight is 4000-18000 g/mol; the preparation method comprises the following steps: mixing succinic acid, butanediol and a catalyst, heating for reaction, heating, adding a phosphorus ion-containing monomer, and carrying out vacuum pumping reaction to obtain the amphiphilic polybutylene succinate ionomer.
4. The healthy and environment-friendly hot melt adhesive as claimed in claim 3, wherein: the phosphorus-containing ionic monomer is 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) potassium phosphate, and is prepared by the following method: mixing p-hydroxybenzaldehyde and phosphoric acid, heating and stirring, adding dihydroxyacetone after the reaction is finished, heating and stirring, adding a KOH solution for salinization after the reaction is finished, and oxidizing with hydrogen peroxide after the salinization to obtain the phosphorus ion-containing monomer 4-carboxyphenyl- (3-hydroxy-2-oxypropyl) potassium phosphate.
5. The amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive according to claim 1, characterized in that: the particle size range of the functional nanoparticles is 20-800 nm; the functional nano particles are at least one of inorganic nano antibacterial powder, inorganic nano formaldehyde removing powder, inorganic nano peculiar smell removing powder and inorganic nano anti-radiation and anti-ultraviolet powder; the inorganic nano antibacterial powder comprises at least one of nano silver powder, nano lanthanum oxide powder, nano zinc oxide powder, nano titanium dioxide powder, nano zeolite powder, nano aluminum oxide powder, nano copper oxide powder, nano magnesium oxide powder and nano silver iodide powder; the inorganic nano formaldehyde-removing powder comprises at least one of nano mineral crystal powder and nano titanium dioxide powder; the inorganic nano peculiar smell removing powder comprises at least one of nano diatomite, nano zinc oxide powder and nano titanium dioxide powder; the inorganic nano anti-radiation and anti-ultraviolet powder comprises at least one of nano titanium dioxide powder, nano zinc oxide powder and nano silicon dioxide powder.
6. The amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive according to claim 1, characterized in that: the functional nano-particles are subjected to surface modification by adopting a silane coupling agent, a titanate coupling agent or an aluminate coupling agent in advance before use.
7. The amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive according to claim 1, characterized in that: 0.1-1 part of functional auxiliary agent is also added into the healthy and environment-friendly hot melt adhesive; the functional auxiliary agent is at least one of plasticizer, antioxidant and anti-aging agent.
8. The preparation method of the amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
weighing the raw material components according to a certain proportion, adding the raw material components into a high-speed mixer, uniformly mixing, then melting and extruding the mixture in a double-screw extruder, and granulating to obtain the healthy and environment-friendly hot melt adhesive.
9. The preparation method of the amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive according to claim 8, characterized by comprising the following steps: the mixing temperature in the high-speed mixer is 65-85 ℃; the temperature of melt extrusion in the double-screw extruder is 140-180 ℃.
10. The application of the amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive in the fields of clothing, bags, daily necessities, furniture and home decoration, automobile decoration and the like.
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to an amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive and preparation and application thereof.
Background
The hot melt adhesive is a solvent-free thermoplastic solid adhesive. When in use, the adhesive is heated and melted to obtain fluidity, wets the surface of an adherend, can be bonded by hard fixation or reaction solidification after being cooled, does not contain a solvent, is nontoxic and tasteless, and belongs to an environment-friendly chemical product. The hot melt adhesive has wide application in the fields of various industries such as clothes, bags, daily necessities, furniture and home furnishings, automobile decoration and the like, the market has higher and higher requirements on the adhesive property such as adhesive strength, weather resistance and the like, meanwhile, the requirements on the opening time, curing rate and the like of the hot melt adhesive are also provided, and the development of high-performance hot melt adhesive products meets the market requirements.
APAO (Amorphous α -olefin copolymer) is a low molecular weight Amorphous plastomer material formed from a-olefins by polymerization and is in a microstructure of an Amorphous, random arrangement, which is unique to many crystalline polymers and thus unique in its application. One important role is as an adhesive and coating component, APAO being mainly hot melt adhesives, paper laminants, sealants. However, the hot melt adhesive containing APAO as the main component has weak polarity, so that the hot melt adhesive has weak bonding capability to a non-polar interface and is easy to fall off after solidification.
Ionic polymers, abbreviated ionomers, refer to polymers that contain small amounts (typically <15 mol%) of ionic groups on the side chains of the molecule. The existence of positive and negative ion pairs in the ionomer can lead the molecules to form strong ionic bonds through the actions of static electricity, ion-dipole and the like; the main chain and the ion side group of the ionomer are subjected to microphase separation to form a nano-scale ion aggregate (ioniggregate) which plays a role in physical crosslinking. The physical crosslinking effect in the ionomer can greatly improve the melt strength, mechanical strength, toughness, tear resistance and the like of the polymer. The physical crosslinking function also has very excellent characteristics, on one hand, at a lower temperature (use temperature), a three-dimensional network structure is formed through crosslinking, and the performance of the material is improved; on the other hand, at higher temperatures (processing temperatures), high temperatures disrupt cluster aggregation and disrupt crosslinking, making it easier to process. Polybutylene succinate (PBS) is a semi-crystalline aliphatic polyester derived from biological substrates, has good thermoplasticity, molecular flexibility and biodegradability, and becomes one of the aliphatic polyesters with the most development potential.
Related project groups of the application have disclosed preparation and application of poly (butylene succinate) ionomer (for example, CN 105061797A poly (butylene succinate) ionomer microporous foamed material and a preparation method thereof, CN 107459637A poly (butylene succinate) ionomer with low molecular weight and high melt viscosity and preparation thereof and microporous foamed material based on the same and an application thereof, CN 110204687A heat-conducting poly (butylene succinate) ionomer and a preparation method and an application thereof, and CN 110343286A poly (butylene succinate) ionomer foam and a preparation method and an application thereof). However, the preparation of novel polybutylene succinate ionomers and their use in hot melt adhesives have not been reported at present.
In addition, most of the existing hot melt adhesives in the current market only can achieve the bonding effect, and the functions of the hot melt adhesives are single. Along with the improvement of living standard, the requirements of people on materials are higher and higher, so that the development of high-quality and high-added-value hot melt adhesive products meets the market demand.
Disclosure of Invention
Aiming at the prior art, the primary object of the invention is to provide an amphiphilic ionomer-reinforced healthy and environment-friendly hot melt adhesive and a preparation method and application thereof.
The invention also aims to provide a preparation method of the amphiphilic polybutylene succinate ionomer.
In order to achieve the purpose, the invention provides the following technical scheme:
an amphiphilic ionomer-reinforced healthy environment-friendly hot melt adhesive comprises the following raw material components in parts by weight:
further, the tackifying resin is at least one of rosin resin, terpene resin and terpene phenolic resin.
Further, an ionic monomer in the amphiphilic polybutylene succinate ionomer is a phosphorus-containing ionic monomer, the ionic molar concentration of the monomer is 1% -10%, and the number average molecular weight of the monomer is 4000-18000 g/mol; the preparation method comprises the following steps:
mixing Succinic Acid (SA), Butanediol (BD) and a catalyst, heating for reaction, heating, adding a phosphorus-ion-containing monomer, and vacuumizing for reaction to obtain the amphiphilic polybutylene succinate ionomer (PBSIx, wherein x is the mole fraction of the ion monomer).
The method of the invention obtains the amphiphilic polybutylene succinate ionomer by a melt polycondensation method.
The mol ratio of the succinic acid to the butanediol is 1: 1.05-1: 1.55, preferably 1: 1.2.
The molar ratio of the phosphorus-containing ionic monomer to the succinic acid is 0-5: 100, preferably 5: 100.
The catalyst can be tetrabutyl titanate and other catalysts conventionally used in the field, and the catalyst can be used in a catalytic amount.
The heating reaction is preferably a heat preservation reaction when the temperature is increased to 180 ℃; the time for heating the reaction is preferably such that the by-product water collected is close to the theoretical value.
The temperature rise is preferably to 220 ℃ for reaction for 1 h.
The time for the vacuum pumping reaction is preferably 1 h.
The above reaction is preferably carried out under nitrogen protection.
Preferably, the phosphorus ion-containing monomer is 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) potassium phosphate, which is prepared by the following method: mixing p-hydroxybenzaldehyde and phosphoric acid, heating and stirring, adding dihydroxyacetone after the reaction is finished, heating and stirring, adding a KOH solution for salinization after the reaction is finished, and oxidizing with hydrogen peroxide after the salinization to obtain the phosphorus ion-containing monomer 4-carboxyphenyl- (3-hydroxy-2-oxypropyl) potassium phosphate.
The molar ratio of p-hydroxybenzaldehyde to phosphoric acid used is 2: 1.
The p-hydroxybenzaldehyde and the phosphoric acid are heated to 136 ℃ and stirred to react until a climbing effect appears, the p-hydroxybenzaldehyde is preferably preheated to 116 ℃ until the p-hydroxybenzaldehyde is molten before heating and stirring, and the product is 4-formylphenyl dihydrogen phosphate which is marked as
The molar ratio of dihydroxyacetone to p-hydroxybenzaldehyde is preferably 1:1.
The heating and stirring after adding the dihydroxyacetone means heating to 90 ℃ to react until the system becomes viscous and even generates a rod climbing effect, preferably the stirring speed is 150r/min, the reaction time is 3h, and the product is 4-formylphenyl- (3-hydroxy-2-oxopropyl) hydrogen phosphate which is marked as product 2.
The KOH solution is 5 wt% KOH solution, the molar ratio of KOH to p-hydroxybenzaldehyde is 1:5, the salinization is preferably carried out for 1.5h at 50 ℃, and the product is 4-formylphenyl- (3-hydroxy-2-oxypropyl) potassium phosphate, which is marked as product 3.
The hydrogen peroxide is a 30% hydrogen peroxide solution, the oxidation is preferably carried out for 5 hours at 50 ℃, and the product is 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) potassium phosphate which is marked as product 4.
The amphiphilic polybutylene succinate ionomer prepared by the method still has higher melt viscosity under the condition that the molecular weight is only 4k-8 k.
Furthermore, the particle size range of the functional nanoparticles is 20-800 nm.
Further, the functional nano particles are at least one of inorganic nano antibacterial powder, inorganic nano formaldehyde removing powder, inorganic nano peculiar smell removing powder and inorganic nano anti-radiation and anti-ultraviolet powder; the inorganic nano antibacterial powder comprises at least one of nano silver powder, nano lanthanum oxide powder, nano zinc oxide powder, nano titanium dioxide powder, nano zeolite powder, nano aluminum oxide powder, nano copper oxide powder, nano magnesium oxide powder and nano silver iodide powder; the inorganic nano formaldehyde-removing powder comprises at least one of nano mineral crystal powder and nano titanium dioxide powder; the inorganic nano peculiar smell removing powder comprises at least one of nano diatomite, nano zinc oxide powder and nano titanium dioxide powder; the inorganic nano anti-radiation and anti-ultraviolet powder comprises at least one of nano titanium dioxide powder, nano zinc oxide powder and nano silicon dioxide powder.
Further, the functional nanoparticles are surface-modified with a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent in advance before use.
Further, 0.1-1 part of functional auxiliary agent is added into the healthy and environment-friendly hot melt adhesive; the functional auxiliary agent is at least one of plasticizer, antioxidant and anti-aging agent.
The preparation method of the health and environment-friendly hot melt adhesive reinforced by the amphiphilic ionomer comprises the following steps:
weighing the raw material components according to a certain proportion, adding the raw material components into a high-speed mixer, uniformly mixing, then melting and extruding the mixture in a double-screw extruder, and granulating to obtain the healthy and environment-friendly hot melt adhesive.
Further, the mixing temperature in the high-speed mixer is 65-85 ℃; the temperature of melt extrusion in the double-screw extruder is 140-180 ℃.
The ionomer-enhanced healthy environment-friendly hot melt adhesive is applied to product bonding in the fields of clothing, bags, daily necessities, furniture and home furnishings, automobile decoration and the like.
The amphiphilic polybutylene succinate ionomer used in the invention is a product obtained by condensation polymerization of succinic acid, butanediol and an amphiphilic ionic monomer, wherein the amphiphilic ionic monomer can be a phosphate ionic monomer. The addition of the polybutylene succinate ionomer is a method for improving the adhesive property of the APAO hot melt adhesive. The strong polar group on the ionomer can enable molecules on the APAO and the nonpolar interface to be bonded to generate an induced dipole, and an induced force stronger than a dispersion force is formed, so that the bonding effect is enhanced, and the peel strength is improved. Meanwhile, the effect exists between the APAO and the SBS resin, the compatibility of the APAO and the SBS is increased, and the overall mechanical strength of the hot melt adhesive is improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention innovatively adopts the amphiphilic poly (butylene succinate) ionomer as the tackifier and the plasticizer of the APAO resin, influences the changes of APAO crystal form, melt viscosity and condensed structure, and further improves the wetting property, the peel strength and the bonding property of the APAO resin on different polar surfaces.
(2) According to the invention, the inorganic nano powder with antibacterial, formaldehyde removing, peculiar smell removing, radiation resisting and ultraviolet preventing functions is added into the hot melt adhesive, so that the corresponding health functions of the hot melt adhesive can be endowed, and the additional value of the hot melt adhesive is improved.
(3) The added inorganic nano particles have the health function of the inorganic nano particles, and the added inorganic nano particles have the function of fillers when being added into the hot melt adhesive system with the specific composition, so that the adhesive strength and the weather resistance of the colloid are enhanced.
(4) The invention can further carry out surface coupling modification on the functional nano particles, can improve the physical dispersion effect of the inorganic functional nano particles in the hot melt adhesive, effectively prevents the agglomeration phenomenon of the inorganic nano particles and better plays the functional role of the nano particles.
Drawings
FIG. 1 is a reaction scheme showing the synthesis of potassium 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) phosphate as a phosphorus ion-containing monomer used in the present invention.
FIG. 2 is an infrared spectrum of a
FIG. 3 is an infrared spectrum of polybutylene succinate ionomers of different ion contents obtained by the present invention.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to examples and drawings, but the present invention is not limited thereto. 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.
The amphiphilic polybutylene succinate ionomer used in the following examples was prepared by the following method:
mixing Succinic Acid (SA) and Butanediol (BD) (the molar ratio of the succinic acid to the butanediol is 1:1.2) with a catalytic amount of tetrabutyl titanate, heating to 180 ℃ under the protection of nitrogen, keeping the temperature, reacting until the collected byproduct water is close to a theoretical value, heating to 220 ℃ for 1h, adding a phosphorus ion-containing monomer 4-carboxyphenyl- (3-hydroxy-2-oxypropyl) potassium phosphate (the molar ratio of the phosphorus ion-containing monomer to the succinic acid is 5:100), and vacuumizing for 1h to obtain the amphiphilic polybutylene succinate ionomer (PBSI 5).
The phosphorus ion-containing monomer 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) potassium phosphate is prepared by the following method: the p-hydroxybenzaldehyde is preheated to 116 ℃ until being melted, then mixed with phosphoric acid (the molar ratio of the p-hydroxybenzaldehyde to the phosphoric acid is 2:1), heated to 136 ℃ and stirred for reaction until a climbing effect appears, and the product, namely 4-formylphenyl dihydrogen phosphate, is obtained and is marked as
The reaction route for synthesizing the above phosphorus ion-containing monomer, potassium 4-carboxyphenyl- (3-hydroxy-2-oxopropyl) phosphate, is shown in FIG. 1. The infrared spectra of the