CN101538454A - Adhesive and preparation method thereof - Google Patents
Adhesive and preparation method thereof Download PDFInfo
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- CN101538454A CN101538454A CN200810052462A CN200810052462A CN101538454A CN 101538454 A CN101538454 A CN 101538454A CN 200810052462 A CN200810052462 A CN 200810052462A CN 200810052462 A CN200810052462 A CN 200810052462A CN 101538454 A CN101538454 A CN 101538454A
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- polyhydroxyalkanoate
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- 239000000853 adhesive Substances 0.000 title claims abstract description 14
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- -1 poly(ε - caprolactone) Polymers 0.000 claims abstract description 25
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 23
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 23
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000004626 polylactic acid Substances 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims abstract 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract 2
- 150000007519 polyprotic acids Polymers 0.000 claims abstract 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-Hydroxyoctanoic acid Natural products CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 claims description 2
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 2
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims description 2
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000009941 weaving Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims 1
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical group CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 claims 1
- REKYPYSUBKSCAT-UHFFFAOYSA-N beta-hydroxyvaleric acid Natural products CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 125000002298 terpene group Chemical group 0.000 claims 1
- 235000007586 terpenes Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000000835 fiber Substances 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000033764 rhythmic process Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- KPQQVMAQFYVRFC-UHFFFAOYSA-N 2-hydroxybutanoic acid 2-hydroxyhexanoic acid Chemical compound OC(C(=O)O)CCCC.OC(C(=O)O)CC KPQQVMAQFYVRFC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007518 monoprotic acids Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明公开了一种胶粘剂及其制备方法，更具体地，由基材和改性剂进行反应而得，其中基材为聚羟基脂肪酸酯、聚乳酸、乳酸羟基乙酸共聚物、聚(ε－己内酯)、芳香族聚酯之一或其组合，改性剂为一元酸、多元酸及其酸酐、一元醇、多元醇、多羟基羧基小分子及其酰化或酯化衍生物之一或其组合。本发明公开的胶粘剂具有无毒、可生物降解的优点，可以满足食品包装、生物医学、组织工程和其它用途的需要。The invention discloses an adhesive and a preparation method thereof. More specifically, it is obtained by reacting a base material and a modifying agent, wherein the base material is polyhydroxyalkanoate, polylactic acid, lactic acid glycolic acid copolymer, poly(ε - caprolactone), aromatic polyester or a combination thereof, the modifier is monobasic acid, polybasic acid and its anhydride, monohydric alcohol, polyhydric alcohol, polyhydroxy carboxyl small molecules and their acylated or esterified derivatives one or a combination thereof. The adhesive disclosed by the invention has the advantages of non-toxicity and biodegradability, and can meet the needs of food packaging, biomedicine, tissue engineering and other applications.
Description
Technical field
The present invention relates to a kind of is the tackiness agent and preparation method thereof of base material with macromolecular material.
Background technology
A big chunk classification all contains the solvent that quantity differs in the common tackiness agent, organic solvent causes waste and environmental pollution easily, even make water as solvent, also because solvent evaporates needs the regular hour, thereby set time is longer, and use is caused certain inconvenience and restriction.
Hot melt adhesive is 100% solid owing to do not contain solvent, becomes typical environment-friendly adhesive, need heat fused to become fluid when using because of it after, could be coated with use, hence obtain one's name.The hot melt adhesive that uses in Pressuresensitive Tape and the label is also referred to as hot-fusible pressure-sensitive adhesive.At present commercially available the said products exists complex manufacturing, product performance are irreconcilable and product can only partly be degraded shortcoming.
Aliphatic polyester is most important biodegradable and biocompatible materials, is widely used in agricultural, coating, medicine (drug controllable release, medical embedded material are sewed up agent etc.), tackiness agent and the packaging industry.Most representative in the aliphatic polyester is polyhydroxyalkanoate, poly(lactic acid) and poly-(6-caprolactone).
Microorganism polyhydroxyalkanoate (Polyhydroxyalkanoates is hereinafter to be referred as PHA) is the bioabsorbable polymer material that develops rapidly nearly two more than ten years, it is a polyester in the multiple microbial cell, is a kind of natural, green macromolecular material that structure is changeable.PHA has the excellent biological compatibility energy, the hot workability of biodegradability and plastics, therefore can be used as bio-medical material and biodegradable wrapping material, PHA also has many high added value performances such as non-linear optical property, piezoelectricity, barrier properties for gases.Just because of PHA has compiled these good performances, make it have the potential widespread use in fields such as wrapping material, jointing material, spray material and dress material, utensil class material, electronic product, durable consumer goods, agricultural prods, automated production, chemical mediator and solvents.The performance variation that the diversification of PHA structure, composition structure diversity bring makes it have remarkable advantages in application.Form PHA according to monomer and can be divided into three major types: a class is short chain PHA, as poly butyric ester (PHB) and poly-hydroxyl valerate (PHV) and their copolymer p HBV; Another kind of is middle long-chain PHA, as poly-hydroxycaproic ester (PHHx), poly-Hydroxyoctanoic acid ester (PHO) etc.; The 3rd class is short chain and middle long-chain copolyesters, as hydroxybutyric acid-hydroxycaproic acid copolyesters (PHBHHx).
Polylactic acid PLA (Polylactic acid) is a kind of biodegradable aliphatic polyester, owing to it can obtain being described as " green plastic " from reproducible resource of agricultural such as cereal.Poly(lactic acid) has good thermoplastic processibility, and favorable mechanical performance and degraded parameter are also arranged.Poly(lactic acid) can be processed melt extruding on the machine of PET in tradition and be processed, and product not only has the similar performance with PET, has also increased advantage such as degraded and compost ability completely.Can produce various types of films, fiber or thread fabric with poly(lactic acid), application comprises agricultural/horticultural industry product, soil property surface protection, dress ornament and furnishings, personal hygiene prod, wrapping material and industry etc.In addition, PLA has obtained the approval of various countries hygiene departments already as medical embedded material, has been widely used in clinical.Lactic acid and co-glycolic acid PLGA have further improved the application performance of PLA.
Poly-(6-caprolactone) PCL is a kind of crystalline linear polymer, is a kind of flexible material when the greenhouse, and good ventilation property and the consistency fabulous with other material are arranged.Because its biological degradability, biocompatibility and thermo-elasticity have good potentiality as Biodegradable material and bioengineered tissue material.
Aromatic polyester is meant the macromolecular material that terephthalic acid and dibasic alcohol polycondensation obtain, and mainly comprises the PET that obtains with the ethylene glycol polycondensation, the PBT that obtains with the butyleneglycol polycondensation.Aromatic polyester has very strong toughness, flexibility, agent of low hygroscopicity, low gas permeability, to the high corrosion-resistant and the good insulation performance of pharmaceutical chemicals, is a kind of high-molecule material such as producd fibers, film, engineering plastics, tackiness agent that have been widely used in.The polyster fibre and the polyester film product of current widespread use are to form by aromatic polyester PET is made.Fiber level PET polyester slice is used to make terylene short fiber peacekeeping polyester filament, is the raw material of supplying with polyster fibre enterprise's processing fiber and related products.The PET film serves many purposes, as wrapping material, decorative yarn, battery insulator, industrial belt, tape, sanitary apparatus etc.Aromatic polyester also is widely used in fields such as electronic apparatus, health care, building, automobile as engineering plastics.We can say that aromatic polyester is important intermediates that connect petroleum chemicals and a plurality of industry products.
Above-mentioned dissimilar material has different separately characteristics, is the problem that those skilled in the art puts forth effort to solve but how to utilize these product characteristics to obtain that production technique is simple, product performance are adjustable and have biodegradable hot melt adhesive always.
Summary of the invention
In order to achieve the above object, the present inventor has carried out a large amount of experiments, having obtained a class is the tackiness agent of base material with one of polyhydroxyalkanoate, poly(lactic acid), lactic-co-glycolic acid, poly-(6-caprolactone), aromatic polyester or its composition, and described tackiness agent has advantages such as feed composition is few, production technique is simple, product performance are adjustable, asepsis environment-protecting is biodegradable.
More specifically, the invention discloses:
A kind of tackiness agent, base material are one of polyhydroxyalkanoate, poly(lactic acid), lactic-co-glycolic acid, poly-(6-caprolactone), aromatic polyester or its combination.
Wherein polyhydroxyalkanoate is to be represented by formula (I):
Wherein, m=1,2,3 or 4, common m=1; N represents the polymerization degree; R is alterable height side chain (R can be H, and the structure of from 1 to 18 carbon atom), can be saturated or unsaturated, straight or branched, aliphatics or aromatic group (Chen GQ, Wu Q, Zhao K, Yu HP ﹠amp; Chan A.ChiralBiopolyesters-Polyhydroxyalkanoates Synthesized by Microorganisms.Chinese J ofPolymer Science 18 (2000) 389-396).Described polyhydroxyalkanoate comprises the mixture of homopolymer, multipolymer and their arbitrary proportions of various polyhydroxyalkanoates, and for example short chain PHA is as poly--3-hydroxybutyric acid homopolymer PHB, 3-hydroxybutyric acid and 3-hydroxyl pentanoate copolymer PHBV; Middle long-chain PHA such as 3-hydroxycaproic acid and 3-Hydroxyoctanoic acid copolymer p HHO; Short chain and middle long-chain pha copolymer such as 3-hydroxybutyric acid and 3-hydroxycaproic acid copolymer p HBHHx, and 3-hydroxybutyric acid and 4 hydroxybutyric acid copolymer p (3HB-4HB) or the like.
The molecular structure that can be used for polylactic acid PLA of the present invention, lactic-co-glycolic acid PLGA is respectively by shown in formula (II) and the formula (III):
The molecular structure of poly-(6-caprolactone) can be by shown in the formula (IV):
Aromatic polyester can be worked as R=-CH by shown in the formula V
2CH
2-time is PET, as R=-(CH
2)
4-time is PBT.
On the other hand, the present invention also provides the preparation method of tackiness agent: comprise that with base material with the required tackiness agent of properties-correcting agent prepared in reaction, wherein base material and properties-correcting agent mass ratio are 1: 0.05～2, can add catalyzer if desired.Wherein properties-correcting agent is monoprotic acid, polyprotonic acid and acid anhydrides thereof, monohydroxy-alcohol, polyvalent alcohol, poly-hydroxy carboxyl small molecules and one of acidylate or esterified derivative or its combination; more specifically; can be 2; 2-dimethylol propionic acid, glycerol, Glacial acetic acid; properties-correcting agent mainly is the fragment of small molecular weight with the base material macromolecules degradation, but the also crosslinked or cladodification macromole of generating portion simultaneously.Catalyzer is toluenesulphonic acids, two stannous iso caprylates, SnCl
2, Zn (Ac)
2, Mn (Ac)
2, Sb
2O
3, Mg (Ac)
2, Ti (OBu)
4One of or its combination.Catalyst levels is generally 0.5% of base material total mass, and institute's use temperature is the best use temperature of each catalyzer, and generally between 80 ℃ to 180 ℃, resize ratio can obtain tackiness agent or tackiness agent work in-process.
The preparation method of above-mentioned tackiness agent also is included in preceding one of softening agent, tackifier, the filler or its combination elder generation and matrix of adding of reaction and mixes.Wherein softening agent can be tributyl acetylcitrate ATBC, paraffin, and tackifier can be terpine resin, and filler can be light calcium carbonate.Mixing temperature should be lower than the decomposition temperature of base material, generally between 80 ℃ to 180 ℃.
The reaction that obtains glue paste is included under the nitrogen protection raw material is heated to fusion; under molten state, continue then to stir; can add catalyzer and shorten the reaction times; then cooling promptly, the product that obtains can be again makes up by reacting the glue paste that obtains different performance with one of matrix and softening agent, tackifier, filler or its.
Tackiness agent disclosed by the invention; can be widely used in wood working, building, packing, weaving, paper product, cigarette, the field of light industry; more specifically, at packaging field, can be as preparation trade mark film, double sticky tape, medical adhesive tape, protective tapes, solar film band.Application method is with reference to the application's using method commonly used a few days ago.
Embodiment
As non-special instruction, each components contents is the molar percentage of the total component of each ingredients constitute in the polymkeric substance.
Embodiment 1
Take by weighing the 3g molecular weight and be 380,000 P (3HB-4HB) (4HB content is 20%) multipolymer (Tianjin state rhythm) in three mouthfuls of round-bottomed flasks of 250ml, add 3g 2, the 2-dimethylol propionic acid is made properties-correcting agent.Vacuumize the back inflated with nitrogen, after 3 times, under the nitrogen protection condition, 160 ℃ of constant temperature to raw materials melt are pourable liquid repeatedly.In flask, add catalyzer two stannous iso caprylate 0.15ml with disposable syringe.Under the nitrogen protection under normal pressure condition, react 30min after adding catalyzer, change into then under vacuum condition and react 30min, stop heating, be cooled to room temperature under the nitrogen protection.Prepare the transparent colloid of little Huang, can make tackiness agent and use.
Embodiment 2
Take by weighing the 2g molecular weight and be 440,000 P (3HB-4HB) (4HB content is 40%) multipolymer (Tianjin state rhythm), the 1g molecular weight is 750,000 PHBHHx superpolymer (Guangdong joins hundred million bio-engineering corporations) is in three mouthfuls of round-bottomed flasks of 250ml, add 3g 2,2-dimethylol propionic acid, 0.75g glycerol are made properties-correcting agent.Vacuumize the back inflated with nitrogen, after 3 times, under the nitrogen protection condition, 160 ℃ of constant temperature to raw materials melt are pourable liquid repeatedly.In flask, add catalyzer two stannous iso caprylate 0.15ml with disposable syringe.Be warming up to 170 ℃ behind the adding catalyzer and under the nitrogen protection under normal pressure condition, react 30min, change into then under vacuum condition and react 15min, stop heating, be cooled to room temperature under the nitrogen protection.Prepare shallow white translucent colloid, harder, can make pressure sensitive adhesive and use.
Embodiment 3
Take by weighing the 3g molecular weight and be 490,000 P (3HB-4HB) (4HB content is 20%) multipolymer (Tianjin state rhythm,), the 1g molecular weight is that 500,000 PHB (Jiangsu group of Nan Tian) superpolymer is in three mouthfuls of round-bottomed flasks of 250ml, add 1g 2, the 2-dimethylol propionic acid is made properties-correcting agent.Vacuumize the back inflated with nitrogen, after 3 times, under the nitrogen protection condition, 160 ℃ of constant temperature to raw materials melt are pourable liquid repeatedly.In flask, add catalyzer two stannous iso caprylate 0.2ml with disposable syringe.Be warming up to 160 ℃ behind the adding catalyzer and under the nitrogen protection under normal pressure condition, react 15min, change into then under vacuum condition and react 60min, stop heating, be cooled to room temperature under the nitrogen protection.It is translucent to prepare little yellow, and hard and sticking colloid can be made hot-fusible pressure-sensitive adhesive and use, and softening temperature is about 60 ℃.
Embodiment 4
Taking by weighing the 3.6g molecular weight and be 440,000 P (3HB-4HB) 4HB content is 40%) multipolymer (Tianjin state rhythm, lot number F-40-40) in three mouthfuls of round-bottomed flask of 250ml, add the 1.2g tributyl acetylcitrate, 0.25g Glacial acetic acid, 1.2g terpine resin, 0.2g solid paraffin, and 0.06g antioxidant 1010.Vacuumize the back inflated with nitrogen, after 3 times, under the nitrogen protection condition, 170 ℃ of constant temperature stir 8h repeatedly.Stop heating, be cooled to room temperature under the nitrogen protection.Prepare golden yellow translucent colloid, can directly be coated with and do the pressure sensitive adhesive use.
Embodiment 5
Take by weighing the 5g molecular weight and be 490,000 P (3HB-4HB) (4HB content is 20%) multipolymer (Tianjin state rhythm) in three mouthfuls of round-bottomed flasks of 250ml, add the 2g tributyl acetylcitrate, 0.25g Glacial acetic acid, 0.5g terpine resin.Vacuumize the back inflated with nitrogen, after 3 times, under the nitrogen protection condition, 180 ℃ of constant temperature to raw materials melt are pourable liquid repeatedly.In flask, add catalyzer two stannous iso caprylate 0.25ml with disposable syringe.Be cooled to 170 ℃ behind the adding catalyzer and under the nitrogen protection under normal pressure condition, react 60min, change into then under vacuum condition and react 60min, stop heating, be cooled to room temperature under the nitrogen protection.Prepare yellow translucent colloid, can make hot-fusible pressure-sensitive adhesive and use.
Embodiment 6
Take by weighing the 5.4g molecular weight and be 380,000 P (3HB-4HB) (4HB content is 20%) multipolymer (Tianjin state rhythm), the 0.6g terpine resin, 170 ℃ of melting mixing become the homogeneous mixture under the normal pressure protection of inert gas.Add the product that 12g example 1 method obtains, under the normal pressure protection of inert gas 160 ℃ stir 30min after, be cooled to room temperature.Product is shallow translucent in vain, can make tackiness agent and use.
Provide the foregoing description just in order to demonstrate the invention, rather than for protection scope of the present invention is carried out any restriction.Those skilled in the art are according to spirit of the present invention, and any change that invention is carried out is all within protection scope of the present invention.
Claims (11)
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| CN200810052462A CN101538454A (en) | 2008-03-18 | 2008-03-18 | Adhesive and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106634686A (en) * | 2016-10-10 | 2017-05-10 | 上海金大塑胶有限公司 | Novel environment-friendly adhesive sticker material |
| CN108026427A (en) * | 2015-10-01 | 2018-05-11 | 普拉克生化公司 | Non-reacted hotmelt with specific resin |
| CN109627986A (en) * | 2018-10-15 | 2019-04-16 | 哈尔滨工业大学无锡新材料研究院 | Dedicated degradable adhesive of a kind of glass/metal bonding and preparation method thereof |
| CN109722201A (en) * | 2018-12-26 | 2019-05-07 | 深圳日高胶带新材料有限公司 | A kind of polyester pressure sensitive adhesive that can be biodegradable and its application |
| CN112226191A (en) * | 2020-08-24 | 2021-01-15 | 江苏美境新材料有限公司 | Biodegradable adhesive and preparation method thereof |
| CN118354670A (en) * | 2021-09-15 | 2024-07-16 | 丹尼米尔知识产权有限责任公司 | Biodegradable insect trap |
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2008
- 2008-03-18 CN CN200810052462A patent/CN101538454A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026427A (en) * | 2015-10-01 | 2018-05-11 | 普拉克生化公司 | Non-reacted hotmelt with specific resin |
| CN106634686A (en) * | 2016-10-10 | 2017-05-10 | 上海金大塑胶有限公司 | Novel environment-friendly adhesive sticker material |
| CN109627986A (en) * | 2018-10-15 | 2019-04-16 | 哈尔滨工业大学无锡新材料研究院 | Dedicated degradable adhesive of a kind of glass/metal bonding and preparation method thereof |
| CN109627986B (en) * | 2018-10-15 | 2021-05-25 | 哈尔滨工业大学无锡新材料研究院 | Degradable adhesive special for glass/metal adhesion and preparation method thereof |
| CN109722201A (en) * | 2018-12-26 | 2019-05-07 | 深圳日高胶带新材料有限公司 | A kind of polyester pressure sensitive adhesive that can be biodegradable and its application |
| CN112226191A (en) * | 2020-08-24 | 2021-01-15 | 江苏美境新材料有限公司 | Biodegradable adhesive and preparation method thereof |
| CN118354670A (en) * | 2021-09-15 | 2024-07-16 | 丹尼米尔知识产权有限责任公司 | Biodegradable insect trap |
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