CN113512375A - Method for preparing low-softening-point tackifying resin - Google Patents
Method for preparing low-softening-point tackifying resin Download PDFInfo
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- CN113512375A CN113512375A CN202110793440.7A CN202110793440A CN113512375A CN 113512375 A CN113512375 A CN 113512375A CN 202110793440 A CN202110793440 A CN 202110793440A CN 113512375 A CN113512375 A CN 113512375A
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- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 43
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000025 natural resin Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 99
- 238000010992 reflux Methods 0.000 claims description 89
- 238000003786 synthesis reaction Methods 0.000 claims description 74
- 230000015572 biosynthetic process Effects 0.000 claims description 71
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 30
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 26
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 26
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000003522 acrylic cement Substances 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 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 group 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 claims description 9
- 238000005086 pumping Methods 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 26
- 239000000853 adhesive Substances 0.000 abstract description 23
- 230000001070 adhesive effect Effects 0.000 abstract description 23
- 239000002390 adhesive tape Substances 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 238000005187 foaming Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a low-softening-point tackifying resin and application thereof, wherein the preparation of the low-softening-point tackifying resin comprises the steps of reacting natural resin with dihydric alcohol under a controlled condition, then reacting with glycerol to obtain the low-softening-point tackifying resin, and filling the domestic blank of the preparation of the low-softening-point tackifying resin, wherein the initial adhesion and low-temperature resistance are greatly improved after the prepared low-softening-point tackifying resin is matched with an acrylate adhesive, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesion to nonpolar materials such as PP, PE, PET and the like is obviously improved.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing low-softening-point tackifying resin and application thereof.
Background
Tackifying resins are compounds that increase the tack, especially the surface tack, of adhesive articles, and are widely used in adhesive, coating, and ink formulations, primarily by modification of polymers. The conventional tackifying resin has the characteristics of high softening point and high glass transition temperature. However, the complex acting on the adhesive has poor initial adhesion and low temperature resistance of the prepared acrylic adhesive and poor affinity to non-polar materials (such as PP, PE and PET), so the complex has high requirements on the attached objects and construction operation.
The rosin glyceride is prepared by using rosin as a main raw material and carrying out processes such as decoloration, esterification, stabilization and the like. The softening point on the market is usually above 85 ℃, and some models even reach 140 ℃. The acrylic adhesive is mainly used for hot melt adhesives, coatings and paints, and the prepared acrylic adhesive has poor initial adhesion and weather resistance. Therefore, there is a need for a rosin low-softening-point tackifying resin which has a low softening point, is simple in manufacturing process, and can effectively improve the initial tack and low temperature resistance of an acrylic adhesive.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a synthesis process of low-softening-point tackifying resin, which fills the domestic blank for preparing the low-softening-point tackifying resin.
The invention provides a synthesis process of low-softening-point tackifying resin, which comprises the following steps:
the method comprises the following steps: adding metered natural resin and antioxidant into a synthesis container, vacuumizing, adding nitrogen to protect the natural resin from being oxidized and discolored, and heating to melt the natural resin;
step two: starting stirring, continuously heating until the temperature is raised to a first preset temperature, and adding a catalyst and dihydric alcohol into the synthesis container, wherein the ratio of the catalyst to the dihydric alcohol is 1: 10-15;
step three: dripping dihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and dripping at a dripping speed when the reflux amount is larger than a first preset reflux value until dripping is finished;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is finished after the reflux amount is obviously improved compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to a second predetermined temperature, the second predetermined temperature being greater than the first predetermined temperature;
step six: observing the reflux quantity of the condensing device, and maintaining the temperature to be higher than or equal to a second preset temperature when the reflux quantity of the condensing device is smaller than a second preset reflux quantity value;
step seven: and (3) vacuum-pumping the water refluxed in the synthesis container until the pumped water amount is more than 15-25% of the mass of the low-softening-point tackifying resin, and finishing the reaction.
The low-softening-point tackifying resin prepared by the invention has a softening point of 45-55 ℃, fills up domestic blank tackifying resins, and is characterized by solving the defect that the softening point of the existing tackifying resin is too high, and the adhesive using the tackifying resin can increase the initial viscosity and low temperature resistance, can be used for preparing high-performance adhesive tapes used at low temperature, can greatly improve the bonding strength to non-polar materials such as PP, PE, PET and the like, and can also greatly improve the bonding strength to foaming materials; in addition, after the low-softening-point tackifying resin prepared by the invention is matched with an acrylate adhesive, the initial adhesion and low-temperature resistance are greatly improved, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesive force to non-polar materials such as PP, PE, PET and the like is obviously improved. Preferably, the low-softening-point tackifying resin with the softening point of 55 ℃, the solid content of 100 percent and the color of No. 6 is finally prepared.
Further, the mass ratio of the natural resin, the antioxidant, the catalyst, the dihydric alcohol and the trihydric alcohol is 3000: 5-9: 5-12: 400-500: 60-100. Under the proportion, the reaction difference rate is higher and the cost is lower. Preferably, the mass ratio of the natural resin, the antioxidant, the catalyst, the dihydric alcohol and the trihydric alcohol is 3000: 6: 10: 416: 84. it is to be noted that the amount of the diol is the total amount of the two additions.
Further, the natural resin is rosin resin, and the antioxidant is antioxidant 1010 and/or antioxidant 168. In the embodiment, the antioxidants are the antioxidant 1010 and the antioxidant 168, the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, the antioxidants and the antioxidant 1010 cooperate to generate an antioxidant effect, and the antioxidant effect is better under the condition of equal mass ratio.
Furthermore, the catalyst is phosphoric acid, the dihydric alcohol is diethylene glycol, and the trihydric alcohol is glycerol, so that the cost is reduced, and the requirements of products are met.
Further, the first predetermined temperature is 200 ℃ and 250 ℃, preferably 230 ℃; the second predetermined temperature is 255 ℃ and 280 ℃, preferably 260 ℃; in the sixth step, the temperature is maintained at 255-280 ℃.
Further, the stirring speed is 20-100Hz, preferably 30-50Hz, to facilitate the sufficient mixing and complete the reaction.
Further, the second step: starting stirring, continuously heating until the temperature is raised to a first preset temperature, adding a catalyst and dihydric alcohol into the synthesis container, wherein the ratio of the catalyst to the dihydric alcohol is 1:10-15, and stirring for reaction for 20-60 minutes to ensure that the dihydric alcohol and the natural resin are fully reacted under the catalytic action of the catalyst.
Further, the first predetermined reflux value is set according to actual conditions, in this embodiment, the diol is dripped at a dripping speed when the reflux amount is maximum, the esterification reaction efficiency is highest, the dripping speed is also most reasonable, if the dripping speed is reduced, the reaction efficiency is reduced, if the dripping speed is too fast, because the alcohol consumption heat of the dripping is too fast, the temperature is reduced, and the efficiency is also reduced. The first predetermined backflow amount value may be set to 95% of the maximum backflow amount, but is not limited thereto.
Further, in the fourth step: the reflux quantity is increased by 10-30% compared with the reflux quantity before the trihydric alcohol is dripped, and the corresponding dripping speed is maintained for dripping until the dripping is finished. When the reflux amount is increased by 10-30 percent, namely the reflux amount is obviously increased, the esterification reaction with the trihydric alcohol is started and can be continuously and stably dripped at the speed when being observed by naked eyes.
Further, since the solution is added to the synthesis vessel in all of the second to fourth steps, the temperature in the synthesis vessel is lowered, and thus, in the fifth step, the temperature is raised to the second predetermined temperature to ensure that the synthesis reaction is smoothly performed. Further, the temperature rise rate is limited to the condition that the outlet temperature of the condensing device does not exceed 160 ℃, because when the outlet temperature exceeds 160 ℃, a large amount of dropwise added alcohol is taken out, raw materials are lost, the yield is reduced, and the production is not facilitated.
Further, in the sixth step, the reflux amount of the condensing device is observed, when the reflux amount of the condensing device is smaller than a second preset reflux amount value, which indicates that the reflux amount is small or even no reflux amount, the reaction is basically completed, and the temperature is maintained to be greater than or equal to the second preset temperature so as to perform more sufficient reaction and concentration; and then executing a seventh step, performing vacuum extraction on the water refluxed in the synthesis container until the extracted water amount is more than 15% -25% of the low-softening-point tackifying resin, and finishing the preparation if the water content meets the requirement. Of course, the acid value of the low-softening-point tackifier resin may be measured, and when the acid value is satisfied, the production is completed. The second predetermined backflow value may be set to 10% of the maximum backflow value, but not limited thereto, and the backflow may be almost invisible to the naked eye, which is not described herein again.
In practice, in order to prevent the product from being oxidized by air, the method also comprises a step eight, when the reaction is completed, nitrogen is filled, and the solution in the synthesis container is transferred to a discharging device for storage before the solution is cooled. The solution in the synthesis vessel is transferred before being cooled, considering that the hot reaction product has high fluidity and is easy to transfer, and if the solution is cooled, the product is large in year and is not beneficial to transfer.
Further, the synthesis process of the low-softening-point tackifying resin is applied to the preparation of the acrylic adhesive. After the low-softening-point tackifying resin prepared by the invention is matched with the acrylate adhesive, the initial adhesion and the low-temperature resistance are greatly improved, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesive force on nonpolar materials such as PP, PE and PET and foaming materials is obviously improved.
It should be particularly noted that the acrylic adhesive of the low-softening-point tackifying resin prepared by the method of the present invention has an initial adhesion of less than 5cm, a glass strength of 18N/25mm, and a tack time of more than 24h, and compared with an acrylic adhesive without the low-softening-point tackifying resin of the present invention, the performance is significantly improved, and at the same time, the finished product can be used in a low temperature environment of-40 ℃, and the adhesive force to non-polar materials such as PP, PE, PET, and the like, and foamed materials is significantly improved.
The following are the performance parameters of the finished product prepared by adopting the acrylic adhesive of the low-softening-point tackifying resin prepared by the method of the invention in a low-temperature environment of-40 ℃, and the test results of the adhesive force of the non-polar materials such as PP, PE, PET and the like and the foaming materials.
| Condition | Initial adhesion | Strength of glass | Time sticky |
| -40℃ | 4.5cm | 17N/25mm | 23h |
| PP | 4.8cm | 16.5N/25mm | 24.2h |
| Foamed plastic | 4.9cm | 17.3N/25mm | 23.8h |
| Foam rubber | 4.6cn | 17.6N/25mm | 24.9h |
The technical scheme of the invention can realize the following positive effects:
1. the low-softening-point tackifying resin prepared by the invention fills the domestic blank, and solves the defect of overhigh softening point of the existing tackifying resin;
2. the invention prepares an adhesive which can increase the initial viscosity and low temperature resistance of the adhesive using the tackifying resin.
3. The invention prepares tackifying resin which can greatly improve the bonding strength of non-polar materials such as PP, PE, PET and the like.
4. The tackifying resin prepared by the method can greatly improve the bonding strength of the foaming material.
5. After the low-softening-point tackifying resin prepared by the invention is matched with the acrylate adhesive, the initial adhesion and the low-temperature resistance are greatly improved, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesive force on nonpolar materials such as PP, PE and PET and foaming materials is obviously improved.
Drawings
FIG. 1 is a schematic flow chart of the process for synthesizing a low softening point tackifying resin of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In the description of the present invention, it should be understood that the terms "first", "second", etc. are used to define the components, and are used only for the convenience of distinguishing the corresponding components, and if not otherwise stated, the terms have no special meaning, and thus, should not be construed as limiting the scope of the present invention.
The embodiment of the invention provides a synthesis process of low-softening-point tackifying resin, which comprises the following steps:
the method comprises the following steps: adding metered natural resin and antioxidant into a synthesis container, vacuumizing, adding nitrogen to protect the natural resin from being oxidized and discolored, and heating to melt the natural resin;
step two: starting stirring, continuously heating until the temperature is raised to a first preset temperature, and adding a catalyst and dihydric alcohol into the synthesis container, wherein the ratio of the catalyst to the dihydric alcohol is 1: 10-15;
step three: dripping dihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and dripping at a dripping speed when the reflux amount is larger than a first preset reflux value until dripping is finished;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is finished after the reflux amount is obviously improved compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to a second predetermined temperature, the second predetermined temperature being greater than the first predetermined temperature;
step six: observing the reflux quantity of the condensing device, and maintaining the temperature to be higher than or equal to a second preset temperature when the reflux quantity of the condensing device is smaller than a second preset reflux quantity value;
step seven: and (3) vacuum-pumping the water refluxed in the synthesis container until the pumped water amount is more than 15-25% of the mass of the low-softening-point tackifying resin, and finishing the reaction.
The low-softening-point tackifying resin prepared by the invention has a softening point of 45-55 ℃, fills up domestic blank tackifying resins, and is characterized by solving the defect that the softening point of the existing tackifying resin is too high, and the adhesive using the tackifying resin can increase the initial viscosity and low temperature resistance, can be used for preparing high-performance adhesive tapes used at low temperature, can greatly improve the bonding strength to non-polar materials such as PP, PE, PET and the like, and can also greatly improve the bonding strength to foaming materials; in addition, after the low-softening-point tackifying resin prepared by the invention is matched with an acrylate adhesive, the initial adhesion and low-temperature resistance are greatly improved, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesive force to non-polar materials such as PP, PE, PET and the like is obviously improved. Preferably, the low-softening-point tackifying resin with the softening point of 55 ℃, the solid content of 100 percent and the color of No. 6 is finally prepared.
Further, the mass ratio of the natural resin, the antioxidant, the catalyst, the dihydric alcohol and the trihydric alcohol is 3000: 5-9: 5-12: 400-500: 60-100. Under the proportion, the reaction difference rate is higher and the cost is lower. Preferably, the mass ratio of the natural resin, the antioxidant, the catalyst, the dihydric alcohol and the trihydric alcohol is 3000: 6: 10: 416: 84. it is to be noted that the amount of the diol is the total amount of the two additions.
Further, the natural resin is rosin resin, and the antioxidant is antioxidant 1010 and/or antioxidant 168. In the embodiment, the antioxidants are the antioxidant 1010 and the antioxidant 168, the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:1, the antioxidants and the antioxidant 1010 cooperate to generate an antioxidant effect, and the antioxidant effect is better under the condition of equal mass ratio.
Furthermore, the catalyst is phosphoric acid, the dihydric alcohol is diethylene glycol, and the trihydric alcohol is glycerol, so that the cost is reduced, and the requirements of products are met.
Further, the first predetermined temperature is 200 ℃ and 250 ℃, preferably 230 ℃; the second predetermined temperature is 255 ℃ and 280 ℃, preferably 260 ℃; in the sixth step, the temperature is maintained at 255-280 ℃.
Further, the stirring speed is 20-100Hz, preferably 30-50Hz, to facilitate the sufficient mixing and complete the reaction.
Further, the second step: starting stirring, continuously heating until the temperature is raised to a first preset temperature, adding a catalyst and dihydric alcohol into the synthesis container, wherein the ratio of the catalyst to the dihydric alcohol is 1:10-15, and stirring for reaction for 20-60 minutes to ensure that the dihydric alcohol and the natural resin are fully reacted under the catalytic action of the catalyst.
Further, the first predetermined reflux value is set according to actual conditions, and in this embodiment, the glycol is dripped at a dripping speed at which the reflux amount is maximum. When the backward flow is the biggest, esterification reaction efficiency is the highest, and the dropwise add speed is also the most reasonable, if reduce dropwise add speed, reaction efficiency can reduce, if the dropwise add is too fast, because the dropwise alcohol consumes the caloric power too fast, the temperature can descend, and efficiency also can reduce. The first predetermined backflow amount value may be set to 95% of the maximum backflow amount, but is not limited thereto.
Further, in the fourth step: the reflux quantity is increased by 10-30% compared with the reflux quantity before the trihydric alcohol is dripped, and the corresponding dripping speed is maintained for dripping until the dripping is finished. When the reflux amount is increased by 10-30 percent, namely the reflux amount is obviously increased, the esterification reaction with the trihydric alcohol is started and can be continuously and stably dripped at the speed when being observed by naked eyes.
Further, since the solution is added to the synthesis vessel in all of the second to fourth steps, the temperature in the synthesis vessel is lowered, and thus, in the fifth step, the temperature is raised to the second predetermined temperature to ensure that the synthesis reaction is smoothly performed. Further, the temperature rise rate is limited to the condition that the outlet temperature of the condensing device does not exceed 160 ℃, because when the outlet temperature exceeds 160 ℃, a large amount of dropwise added alcohol is taken out, raw materials are lost, the yield is reduced, and the production is not facilitated.
Further, in the sixth step, the reflux amount of the condensing device is observed, when the reflux amount of the condensing device is smaller than a second preset reflux amount value, which indicates that the reflux amount is small or even no reflux amount, the reaction is basically completed, and the temperature is maintained to be greater than or equal to the second preset temperature so as to perform more sufficient reaction and concentration; and then executing a seventh step, performing vacuum extraction on the water refluxed in the synthesis container until the extracted water amount is more than 15% -25% of the low-softening-point tackifying resin, and finishing the preparation when the water content meets the requirement. Of course, the acid value of the low-softening-point tackifier resin may be measured, and when the acid value is satisfied, the production is completed. The second predetermined backflow value may be set to 10% of the maximum backflow value, but not limited thereto, and the backflow may be almost invisible to the naked eye, which is not described herein again.
In practice, in order to prevent the product from being oxidized by air, the method also comprises a step eight, when the reaction is completed, nitrogen is filled, and the solution in the synthesis container is transferred to a discharging device for storage before the solution is cooled. The solution in the synthesis vessel is transferred before being cooled, considering that the hot reaction product has high fluidity and is easy to transfer, and if the solution is cooled, the product is large in year and is not beneficial to transfer.
Further, the synthesis process of the low-softening-point tackifying resin is applied to the preparation of the acrylic adhesive. After the low-softening-point tackifying resin prepared by the invention is matched with the acrylate adhesive, the initial adhesion and the low-temperature resistance are greatly improved, the prepared adhesive tape can be used in a low-temperature environment of-40 ℃, and the adhesive force on nonpolar materials such as PP, PE and PET and foaming materials is obviously improved.
It should be particularly noted that the acrylic adhesive of the low-softening-point tackifying resin prepared by the method of the invention has an initial adhesion of less than 5cm, a glass strength of 18N/25mm and an hour adhesion of more than 24h, and the performance is significantly improved compared with the acrylic adhesive without the low-softening-point tackifying resin. And meanwhile, the performance is remarkably improved, the prepared finished product can be used in a low-temperature environment of-40 ℃, and the adhesive force to non-polar materials such as PP, PE, PET and the like and foaming materials is remarkably improved.
It should be particularly noted that the acrylic adhesive of the low-softening-point tackifying resin prepared by the method of the present invention has an initial adhesion of less than 5cm, a glass strength of 18N/25mm, and a tack time of more than 24 hours, and compared with an acrylic adhesive without the low-softening-point tackifying resin of the present invention, the performance is significantly improved, and at the same time, the finished product can be used in a low temperature environment of-40 ℃, and the adhesive force to non-polar materials such as PP, PE, PET, and the like and foamed materials is significantly improved.
The following are the performance parameters of the finished product prepared by adopting the acrylic adhesive of the low-softening-point tackifying resin prepared by the method of the invention in a low-temperature environment of-40 ℃, and the test results of the adhesive force of the non-polar materials such as PP, PE, PET and the like and the foaming materials.
Example 1
A synthesis process of low-softening-point tackifying resin comprises the following steps:
step zero: injecting a predetermined amount of glycerol into a glycerol feeding kettle for standby, injecting a predetermined amount of diglycol into a diglycol feeding kettle for standby, injecting a catalyst and diglycol into a catalyst feeding kettle according to a ratio of 1:12 preparing a solution for later use; the mass ratio of rosin, oxidant 1010, 168, phosphoric acid, diethylene glycol (total amount) and glycerol is 3000: 2.5:2.5: 5: 400: 60, adding a solvent to the mixture;
the method comprises the following steps: adding metered rosin and oxidants 1010 and 168 into a synthesis container, vacuumizing, adding nitrogen to protect the rosin from being oxidized and discolored, and heating to melt the rosin;
step two: starting stirring at the stirring speed of 20HZ, continuously heating until the temperature is raised to 200 ℃, adding phosphoric acid and diethylene glycol into the synthesis container, wherein the ratio of the phosphoric acid to the diethylene glycol is 1:10, and reacting for 20 minutes;
step three: dropwise adding diethylene glycol into the synthesis container, observing the reflux amount of the condensing device, and adjusting the dropwise adding speed by taking the maximum reflux amount as a standard until the diethylene glycol is completely dripped;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is completed when the reflux amount is increased by 10% compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to 255 ℃, wherein the temperature raising speed is limited to that the outlet temperature of the condenser does not exceed 150 ℃;
step six: observing the reflux amount of the condensing device, and maintaining the temperature at 260 ℃ when the reflux amount of the condensing device is small or no;
step seven: vacuum pumping the water refluxed in the synthesis container until the pumped water amount is more than 15% of the mass of the low-softening-point tackifying resin, and finishing the preparation;
step eight: and introducing nitrogen, and transferring the solution in the synthesis container to a discharging device for storage before the solution is cooled.
Example 2
A synthesis process of low-softening-point tackifying resin comprises the following steps:
step zero: injecting a predetermined amount of glycerol into a glycerol feeding kettle for standby, injecting a predetermined amount of diglycol into a diglycol feeding kettle for standby, injecting a catalyst and diglycol into a catalyst feeding kettle according to a ratio of 1:12 preparing a solution for later use; the mass ratio of rosin, oxidant 1010, 168, phosphoric acid, diethylene glycol (total amount) and glycerol is 3000: 3:3: 10: 416: 84;
the method comprises the following steps: adding metered rosin and oxidants 1010 and 168 into a synthesis container, vacuumizing, adding nitrogen to protect the rosin from being oxidized and discolored, and heating to melt the rosin;
step two: starting stirring at the stirring speed of 30HZ, continuously heating until the temperature is raised to 230 ℃, adding phosphoric acid and diethylene glycol into the synthesis container, wherein the ratio of the phosphoric acid to the diethylene glycol is 1:12, and reacting for 30 minutes;
step three: dropwise adding diethylene glycol into the synthesis container, observing the reflux amount of the condensing device, and adjusting the dropwise adding speed by taking the maximum reflux amount as a standard until the diethylene glycol is completely dripped;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is completed when the reflux amount is increased by 20% compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to 260 ℃, wherein the temperature raising speed is limited to the condition that the outlet temperature of the condenser does not exceed 160 ℃;
step six: observing the reflux amount of the condensing device, and maintaining the temperature at 265 ℃ when the reflux amount of the condensing device is smaller or has no reflux amount;
step seven: vacuum pumping the water refluxed in the synthesis container until the pumped water amount is more than 20% of the mass of the low-softening-point tackifying resin, and finishing the preparation;
step eight: and introducing nitrogen, and transferring the solution in the synthesis container to a discharging device for storage before the solution is cooled.
Example 3
A synthesis process of low-softening-point tackifying resin comprises the following steps:
step zero: injecting a predetermined amount of glycerol into a glycerol feeding kettle for standby, injecting a predetermined amount of diglycol into a diglycol feeding kettle for standby, injecting a catalyst and diglycol into a catalyst feeding kettle according to a ratio of 1:12 preparing a solution for later use; the mass ratio of rosin, oxidant 1010, 168, phosphoric acid, diethylene glycol (total amount) and glycerol is 3000: 4:4: 8: 450: 90, respectively;
the method comprises the following steps: adding metered rosin and oxidants 1010 and 168 into a synthesis container, vacuumizing, adding nitrogen to protect the rosin from being oxidized and discolored, and heating to melt the rosin;
step two: starting stirring at the stirring speed of 50HZ, continuously heating until the temperature is raised to 250 ℃, adding phosphoric acid and diethylene glycol into the synthesis container, wherein the ratio of the phosphoric acid to the diethylene glycol is 1:15, and reacting for 40 minutes;
step three: dropwise adding diethylene glycol into the synthesis container, observing the reflux amount of the condensing device, and adjusting the dropwise adding speed by taking the maximum reflux amount as a standard until the diethylene glycol is completely dripped;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is completed when the reflux amount is increased by 30% compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to 280 ℃, wherein the temperature raising speed is limited to the condition that the outlet temperature of the condenser does not exceed 170 ℃;
step six: observing the reflux amount of the condensing device, and maintaining the temperature at 290 ℃ when the reflux amount of the condensing device is small or no;
step seven: vacuum pumping the water refluxed in the synthesis container until the pumped water amount is more than 30% of the mass of the low-softening-point tackifying resin, and finishing the preparation;
step eight: and introducing nitrogen, and transferring the solution in the synthesis container to a discharging device for storage before the solution is cooled.
Example 4
A synthesis process of low-softening-point tackifying resin comprises the following steps:
step zero: injecting a predetermined amount of glycerol into a glycerol feeding kettle for standby, injecting a predetermined amount of diglycol into a diglycol feeding kettle for standby, injecting a catalyst and diglycol into a catalyst feeding kettle according to a ratio of 1:12 preparing a solution for later use; the mass ratio of rosin, oxidant 1010, 168, phosphoric acid, diethylene glycol (total amount) and glycerol is 3000: 4.5:4.5: 12: 500: 100, respectively;
the method comprises the following steps: adding metered rosin and oxidants 1010 and 168 into a synthesis container, vacuumizing, adding nitrogen to protect the rosin from being oxidized and discolored, and heating to melt the rosin;
step two: starting stirring at the stirring speed of 20HZ, continuously heating until the temperature is raised to 230 ℃, adding phosphoric acid and diethylene glycol into the synthesis container, wherein the ratio of the phosphoric acid to the diethylene glycol is 1:12, and reacting for 60 minutes;
step three: dropwise adding diethylene glycol into the synthesis container, observing the reflux amount of the condensing device, and adjusting the dropwise adding speed by taking the maximum reflux amount as a standard until the diethylene glycol is completely dripped;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is completed when the reflux amount is increased by 20% compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to 260 ℃, wherein the temperature raising speed is limited to the condition that the outlet temperature of the condenser does not exceed 160 ℃;
step six: observing the reflux amount of the condensing device, and maintaining the temperature at 260 ℃ when the reflux amount of the condensing device is small or no;
step seven: vacuum pumping the water refluxed in the synthesis container until the pumped water amount is more than 20% of the mass of the low-softening-point tackifying resin, and finishing the preparation;
step eight: and introducing nitrogen, and transferring the solution in the synthesis container to a discharging device for storage before the solution is cooled.
Example 5
A synthesis process of low-softening-point tackifying resin comprises the following steps:
step zero: injecting a predetermined amount of glycerol into a glycerol feeding kettle for standby, injecting a predetermined amount of diglycol into a diglycol feeding kettle for standby, injecting a catalyst and diglycol into a catalyst feeding kettle according to a ratio of 1:12 preparing a solution for later use; the mass ratio of rosin, oxidant 1010, 168, phosphoric acid, diethylene glycol (total amount) and glycerol is 3000: 3:3: 12: 420: 88;
the method comprises the following steps: adding metered rosin and oxidants 1010 and 168 into a synthesis container, vacuumizing, adding nitrogen to protect the rosin from being oxidized and discolored, and heating to melt the rosin;
step two: starting stirring at the stirring speed of 30HZ, continuously heating until the temperature is raised to 230 ℃, adding phosphoric acid and diethylene glycol into the synthesis container, wherein the ratio of the phosphoric acid to the diethylene glycol is 1:12, and reacting for 30 minutes;
step three: dropwise adding diethylene glycol into the synthesis container, observing the reflux amount of the condensing device, and adjusting the dropwise adding speed by taking the maximum reflux amount as a standard until the diethylene glycol is completely dripped;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is completed when the reflux amount is increased by 20% compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: raising the temperature to 260 ℃, wherein the temperature raising speed is limited to the condition that the outlet temperature of the condenser does not exceed 160 ℃;
step six: observing the reflux amount of the condensing device, and maintaining the temperature at 265 ℃ when the reflux amount of the condensing device is smaller or has no reflux amount;
step seven: vacuum pumping the water refluxed in the synthesis container until the pumped water amount is more than 25% of the mass of the low-softening-point tackifying resin, and finishing the preparation;
step eight: and introducing nitrogen, and transferring the solution in the synthesis container to a discharging device for storage before the solution is cooled.
Claims (10)
1. A synthesis process of tackifying resin with low softening point is characterized by comprising the following steps:
the method comprises the following steps: adding metered natural resin and antioxidant into a synthesis container, vacuumizing, adding nitrogen to protect the natural resin from being oxidized and discolored, and heating to melt the natural resin;
step two: starting stirring, continuously heating until the temperature is raised to a first preset temperature, and adding a catalyst and dihydric alcohol into the synthesis container, wherein the ratio of the catalyst to the dihydric alcohol is 1: 10-15;
step three: dripping dihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and dripping at a dripping speed when the reflux amount is larger than a first preset reflux value until dripping is finished;
step four: dropwise adding the trihydric alcohol into the synthesis container, observing the reflux amount of the condensing device, and maintaining the corresponding dropwise adding speed for dropwise adding until the dropwise adding is finished after the reflux amount is increased compared with the reflux amount before the trihydric alcohol is dropwise added;
step five: increasing the temperature to a second predetermined temperature, the second predetermined temperature being greater than the first predetermined temperature;
step six: observing the reflux quantity of the condensing device, and maintaining the temperature to be higher than or equal to a second preset temperature when the reflux quantity of the condensing device is smaller than a second preset reflux quantity value;
step seven: and (3) vacuum-pumping the water refluxed in the synthesis container until the pumped water amount is more than 15-25% of the mass of the low-softening-point tackifying resin, and finishing the preparation.
2. The synthetic process of claim 1 wherein the mass ratio of the natural resin, the antioxidant, the catalyst, the diol, and the triol is 3000: 5-9: 5-12: 400-500: 60-100.
3. The process of claim 1, wherein the natural resin is rosin and the antioxidant is antioxidant 1010 and/or antioxidant 168.
4. The synthesis process of claim 1, wherein the first predetermined temperature is 200-250 ℃, the second predetermined temperature is 255-280 ℃, and the temperature is maintained at 255-280 ℃ in the sixth step.
5. The process of claim 1, wherein the catalyst is phosphoric acid, the diol is diethylene glycol, and the triol is glycerol.
6. The synthetic process of claim 1 wherein step three: the dropping was carried out at the dropping rate at which the reflux amount was maximized.
7. The process of claim 1, wherein in step four: the reflux quantity is increased by 10-30% compared with the reflux quantity before the trihydric alcohol is dripped, and the corresponding dripping speed is maintained for dripping until the dripping is finished.
8. The process of claim 1, wherein the low softening point tackifying resin has a softening point temperature of 45 to 55 degrees celsius.
9. The process of claim 1, further comprising the step eight of introducing nitrogen and transferring the solution to a holding means for storage before the solution in the synthesis vessel is cooled.
10. Use of a process for the synthesis of a low softening point tackifying resin of any one of claims 1 to 9 in the preparation of an acrylic adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116656265A (en) * | 2023-06-28 | 2023-08-29 | 江苏晶华新材料科技有限公司 | Low-temperature adhesive tape |
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