CN115745800A - Rosin-based crosslinking agent, preparation method thereof and application of pressure-sensitive adhesive - Google Patents
Rosin-based crosslinking agent, preparation method thereof and application of pressure-sensitive adhesive Download PDFInfo
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Abstract
The invention provides a rosin-based crosslinking agent, a preparation method thereof and application of the rosin-based crosslinking agent to a pressure-sensitive adhesive. The UV-cured solvent-free branched acrylate pressure-sensitive adhesive is synthesized by taking an acrylate monomer as a raw material and a rosinyl pentaerythritol triacrylate monomer as a cross-linking agent in a photoinitiation system. The rosin-based acrylate has good solubility, can be used as a multifunctional branched molecular cross-linking agent or a free radical polymerization monomer, improves the additional value of rosin, and widens the application range of the rosin. The preparation method of the pressure-sensitive adhesive is simple, mild, green and efficient, integrates the advantages of acrylate, no solvent, UV ultraviolet curing and branched polymer network structure, and meets the requirements of daily pressure-sensitive adhesive products on environmental protection, no solvent, quick curing, high adhesive force and cohesive force.
Description
Technical Field
The invention relates to a rosin-based crosslinking agent, and in particular relates to a rosin-based crosslinking agent, a preparation method thereof and application of a pressure-sensitive adhesive.
Background
With the increasing shortage of petroleum resources, renewable "green" materials, such as starch, cellulose, lignin and rosin, have the advantages of low cost, renewability, no environmental pollution, biodegradability and the like, and have recently received wide attention at home and abroad. The rosin is an important renewable forest resource, the annual yield of the whole world is about 120 ten thousand tons, and the structure of the rosin is monocarboxylic acid containing two double bonds and having a ternary phenanthrene framework, so that an active site is provided for chemical modification. At present, rosin and derivatives thereof are used as high polymer material, which is another important research for increasing the added value of rosin.
Branched polymers are of great interest to the polymer science community because of their unique physicochemical properties, are structurally not as regular and symmetrical as linear polymers, and are a transition structure between linear and dendritic polymers. The branched polymer pressure-sensitive adhesive has a three-dimensional sphere-like or net-like structure, so that the application performance of the pressure-sensitive adhesive is improved, and the construction of a novel pressure-sensitive adhesive material structure is greatly promoted. Therefore, based on the concept of molecular design, the rosin-based crosslinking agent with a branched structure, which has a group and a structure different from those of the traditional petroleum-based crosslinking agent, is designed, so that the optimal crosslinking effect is expected to be achieved, and the improvement of the comprehensive performance of the pressure-sensitive adhesive and the high-value utilization of rosin are very important.
Meanwhile, with the increasing strictness of environmental regulations, the development of low-pollution or pollution-free environment-friendly adhesives is imperative. Research and development of Ultraviolet (UV) bulk-polymerizable adhesives has brought new eosin to the pressure sensitive adhesive product industry. Chinese patent CN 109111878A discloses a solvent-free ultraviolet dual-curing hot melt pressure-sensitive adhesive, which is prepared by taking ethyl acetate as a solvent, keeping the monomer polymerization reaction at 80 ℃ for 8 hours, adding a cationic photoinitiator (triarylsulfur hexafluoroantimonate), and uniformly stirring for 15 minutes. And finally, gradually raising the temperature to carry out solvent devolatilization, and preparing a solvent-free sample of the cationic ultraviolet-curable (methyl) acrylate copolymer. It can be seen that the organic solvent is still used in the preparation of the photo-curing prepolymer at present, the residual solvent can cause skin irritation if the solvent is not dried in the coating process, and the reaction condition is harsh (80 ℃), and takes long time (8 h).
Therefore, more and more attention is paid to the preparation of the environment-friendly bio-based multi-branched acrylate pressure-sensitive adhesive by adopting a convenient, mild and efficient method.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a cross-linking agent and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a rosin-based cross-linking agent is rosinyl pentaerythritol triacrylate, and has a structural formula as follows:
the preparation method of the cross-linking agent comprises the following steps:
a1, reacting rosin and oxalyl chloride in a good solvent to obtain rosin acyl chloride;
and A2, dripping a solution containing pentaerythritol triacrylate (PETA), an acid-binding agent and a polymerization inhibitor in a certain molar ratio into rosin acyl chloride for esterification reaction to obtain the rosinyl pentaerythritol triacrylate.
Further, in the step A1, the molar ratio of the rosin to the oxalyl chloride is 1: 1-2; the reaction temperature is 0-40 ℃, and the reaction time is 1-8 h;
the good solvent is one of dichloromethane, tetrahydrofuran and ethyl acetate.
Further, in the step A2, the molar ratio of the rosin acyl chloride, the PETA, the acid-binding agent and the polymerization inhibitor is 1:1: 1.2-1.5: 0.01 to 0.05; the esterification reaction temperature is 20-50 ℃, and the reaction time is 4-12 h;
the acid-binding agent is any one of 4-dimethylamino pyridine, triethylamine, pyridine and sodium bicarbonate;
the polymerization inhibitor is any one of hydroquinone, p-hydroxyanisole and p-benzoquinone;
the solution is any one of dichloromethane, tetrahydrofuran, ethyl acetate, toluene and N, N-dimethylformamide.
The cross-linking agent is applied to the preparation of colloid.
A preparation method of a UV light-cured solvent-free branched acrylate pressure-sensitive adhesive comprises the following steps:
b1, adding a certain mass of acrylate soft monomer, acrylate hard monomer and photoinitiator into the crosslinking agent, mixing, stirring, purging with nitrogen, irradiating with ultraviolet light to initiate monomer polymerization, and reacting for a certain time to obtain a pressure-sensitive adhesive prepolymer;
and B2, coating the pressure-sensitive adhesive prepolymer on a polyethylene terephthalate film, and carrying out ultraviolet curing to obtain the UV light-cured solvent-free branched acrylate pressure-sensitive adhesive tape.
Further, in the step B1, the mass ratio of the acrylate hard monomer to the acrylate soft monomer to the abietyl pentaerythritol triacrylate to the photoinitiator is 1:1 to 9:0.25 to 1:0.25 to 1;
the acrylate soft monomer is lauryl methacrylate;
the acrylate hard monomer is any one of tetrahydrofurfuryl methacrylate, butyl methacrylate and isobornyl acrylate;
the photoinitiator is any one of xylene ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
Further, the mixture and the stirring in the step B1 are placed in a transparent bottle, and ultraviolet light is irradiated from the bottom of the transparent bottle;
the nitrogen purging time is 20min, and the ultraviolet light intensity is 0.02mW cm -2 The reaction temperature is room temperature, and the reaction time is 5-30 min.
Further, the illumination intensity of the ultraviolet light curing in the step B2 is 50-100 mW cm -2 The illumination time is 3-10 min.
Furthermore, the adhesive layer of the adhesive tape is10 to 100 μm thick.
The invention has the advantages that:
the rosin-based acrylate with the branched structure provided by the invention has good solubility, and can be used as a multifunctional branched molecular cross-linking agent or a free radical polymerization monomer, so that the additional value of rosin is further improved, and the application range of the rosin is expanded.
The UV ultraviolet-cured solvent-free branched crosslinked acrylate pressure-sensitive adhesive is prepared by taking rosin-based acrylate as a crosslinking agent, and integrates the advantages of acrylate, no solvent, UV ultraviolet curing and branched polymer network structure, so that the initial adhesion of the prepared pressure-sensitive adhesive product can still reach more than 10N, and the requirements of daily pressure-sensitive adhesive products on environmental protection, no solvent, quick curing, high adhesion and cohesion can be met. The method for preparing the pressure-sensitive adhesive is simple, mild, green and efficient, effectively solves the problems that the existing solvent-free pressure-sensitive adhesive has harsh reaction conditions and long time consumption, and organic solvent is still remained when preparing a photo-cured prepolymer, and has strong practicability and wide applicability.
Drawings
FIG. 1 is an infrared spectrum of rosin, rosin acyl chloride and abietyl pentaerythritol triacrylate.
FIG. 2 shows rosin and rosinyl pentaerythritol triacrylate 1 H NMR chart.
Fig. 3 shows the performance of pressure-sensitive adhesive tapes with different amounts of crosslinker.
FIG. 4 is a graph of the infrared spectra of pressure sensitive adhesive prepolymers for different UV cure times.
FIG. 5 is a graph of pressure sensitive adhesive precursor UV cure time, double bond conversion and viscosity.
FIG. 6 is a comparison of the crosslinking performance of a rosinyl pentaerythritol triacrylate (DAPETA) versus a commercial amine-modified epoxy acrylate (AgiSyn 703) and bisphenol A epoxy acrylate (RJ 313) copolymer.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
The reagents used in this example are all commercially available.
The instrument and the detection method used for the test are as follows:
infrared equipment: nicolet iS10 fourier infrared spectrum analyzer (FT-IR), seimer fisher technologies;
nuclear magnetic equipment: bruker400MHz nuclear magnetic resonance NMR spectrometer, brueck, germany;
and (3) viscosity testing: the viscosity of the pressure-sensitive adhesive prepolymer was measured by a Brookfield DV-II + PRO viscometer, BROOKFIELD, USA, using the GB/T2794-2013 method, and the temperature of the sample was kept at 25 ℃. + -. 0.25 ℃ during the test.
And (3) testing the peel strength: an LT-3000 annular initial adhesion tester, sanquan Mizhongshi Co., ltd, for testing the initial adhesion performance of the pressure-sensitive adhesive tape according to the-GB/T31125-2014 annular initial adhesion test method; the CZY-6S holds and glues the tester, and the new accurate apparatus of Jinan of Ji equipment Limited company, according to GB/T4851-1998 method test pressure-sensitive adhesive and hold and glue the performance; XLW (EC) -A stretcher, dennam Languang electromechanical technology, inc., tested the 180 DEG peel strength of a pressure-sensitive adhesive tape according to GB/T2792-1981.
The rosin-based crosslinking agent is rosinyl pentaerythritol triacrylate, and has the following structural formula:
the preparation method of the abietyl pentaerythritol triacrylate comprises the following steps:
a1, according to 1: 1-2, reacting rosin and oxalyl chloride in a good solvent at 0-40 ℃ for 1-8 h to obtain rosin acyl chloride; the good solvent can be any one of dichloromethane, tetrahydrofuran and ethyl acetate.
A2, according to the proportion of 1:1: 1.2-1.5: 0.01-0.05, dripping solution containing pentaerythritol triacrylate (PETA), acid-binding agent and polymerization inhibitor into rosin acyl chloride, carrying out esterification reaction for 4-12 h at 20-50 ℃, washing and drying to obtain the abietyl pentaerythritol triacrylate.
Wherein the acid-binding agent can be any one of 4-dimethylamino pyridine, triethylamine, pyridine and sodium bicarbonate; the polymerization inhibitor can be any one of hydroquinone, p-hydroxyanisole and p-benzoquinone; the solution may be selected from any one of dichloromethane, tetrahydrofuran, ethyl acetate, toluene, and N, N-dimethylformamide.
A preparation method of a UV photocuring solvent-free branched acrylate pressure-sensitive adhesive comprises the following steps:
b1, according to the weight ratio of 0.25-1: 1:1 to 9: 0.25-1, adding acrylate soft monomer, acrylate hard monomer and photoinitiator into abietyl pentaerythritol triacrylate, mixing, adding into a round bottom flask with a stirring device, purging with nitrogen for 20min, and using a UV LED light source at 0.02mW cm -2 The monomer is initiated to polymerize by the light intensity irradiation, and the light source is closed after the reaction is carried out for 5 to 30min at room temperature, so as to obtain the pressure-sensitive adhesive prepolymer.
Wherein the soft acrylate monomer is lauryl methacrylate; the acrylate hard monomer is any one of tetrahydrofurfuryl methacrylate, butyl methacrylate and isobornyl acrylate; the photoinitiator is any one of xylene ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
B2, coating the pressure-sensitive adhesive precursor polymer on polyethylene terephthalateContinuously on a glycol ester film with the light intensity of 50-100 mW cm -2 The light irradiation is carried out for 3-10 min under the light curing machine until the double bonds are completely converted, and the UV light curing solvent-free branched acrylate pressure-sensitive adhesive tape with the adhesive layer thickness of 10-100 mu m is obtained.
Example 1
Preparation of abietyl pentaerythritol triacrylate:
(1) Dissolving 3g (0.01 mol) of rosin monomer (DA) in 25ml of dichloromethane, dropwise adding 1.26g (0.01 mol) of oxalyl chloride into the solution under the condition of ice-water bath, continuously heating to 40 ℃ for reaction for 5 hours, and removing the solvent and unreacted oxalyl chloride by a rotary evaporator after the reaction is finished to obtain rosin acyl chloride monomer;
(2) Dripping the rosin acyl chloride obtained in the step into a tetrahydrofuran (50 mL) solution containing 1.3g (0.01 mol) of pentaerythritol triacrylate (PETA), 1.0g of sodium bicarbonate and 0.01g of hydroquinone under the condition of ice-water bath to react for 30min, heating to 50 ℃, continuing to react for 12h, centrifuging after the reaction is finished to obtain a supernatant, washing the supernatant with absolute ethyl alcohol until the supernatant is colorless, completely removing the unreacted rosin acyl chloride, finally washing with n-hexane, and drying in vacuum at 40 ℃ until the mass is constant to obtain the rosinyl pentaerythritol triacrylate cross-linking agent (DAPETA).
Preparing UV photocuring solvent-free branched acrylate pressure-sensitive adhesive:
(1) Pressure-sensitive adhesive prepolymers were prepared at various DAPETA crosslinker loadings (0,2.5%, 5%,7.5%, 10%) as shown in table 1.
Taking DAPETA2.5% as an example, 0.25g of abietyl pentaerythritol triacrylate, 9g of lauryl methacrylate, 1g of tetrahydrofurfuryl methacrylate and 0.25g of photoinitiator (2-hydroxy-2-methyl-1-phenylpropanone) were mixed and introduced into a round-bottomed flask with stirring, purged with nitrogen for 20min and then irradiated with light at a intensity of 0.02mW/cm -2 The UV LED light source irradiates from the bottom of the round-bottom flask to initiate monomer polymerization for 15min to obtain a pressure-sensitive adhesive prepolymer for subsequent pressure-sensitive adhesive tape experiments.
(2) The pressure-sensitive adhesive precursor obtained above was coated on a polyethylene terephthalate film, and the light intensity was continued at 80mW cm -2 And (3) irradiating the adhesive tape for 5min by a photocuring machine until double bonds are completely converted to obtain the UV photocuring solvent-free branched acrylate pressure-sensitive adhesive tape with the adhesive layer thickness of 25 mu m.
Wherein the infrared spectrogram of rosin, rosin acyl chloride and rosinyl pentaerythritol triacrylate is shown in FIG. 1, and the infrared spectrogram in rosin is 1686cm -1 The peak is vibration absorption peak of carboxyl C = O, and the carboxyl C = O in the rosin molecule is 1782cm after esterification by oxalyl chloride -1 The shock absorption peak disappeared, while the strong shock absorption peak of C = O in the acid chloride appeared, indicating that the acid chlorination reaction was complete. Meanwhile, in PETA, 1637cm -1 Is the absorption peak of the unsaturated double bond; after the esterification reaction, the infrared spectrogram of the target product DAPETA is 1725cm -1 A strong carbonyl stretching vibration peak appears. At the same time, 1636cm -1 The absorption peak of the unsaturated double bond of PETA appears at the position of the peak, so that the successful synthesis of the DAPETA can be preliminarily judged.
To further verify the structure of DAPETA, use was made of 1 The structure was analyzed by H NMR, and FIG. 2 is a nuclear magnetic hydrogen spectrum of rosin and DAPETA. As can be seen from FIG. 2, the chemical shift of the proton at the unsaturated double bond in the tricyclic phenanthrene structure of rosin is mainly at the peak between 6.85 and 7.35. Three new displacement peaks appearing at 5.83,6.19 and 6.41 in the DAPETA spectrogram are the proton chemical shifts of unsaturated double bonds on PETA, and peaks between 4.18 and 4.30 are the proton chemical shifts of three methylene groups connected with ester bonds, which further confirms the successful preparation of the rosinyl pentaerythritol triacrylate crosslinking agent.
In example 1, the properties of the pressure-sensitive adhesive obtained with different amounts of crosslinker are shown in FIG. 3. From the above, the viscosity of the prepolymer reached the coating process after the ultraviolet lamp irradiation for 15min, and then further light irradiation was carried out until the reaction was completed, and the results of experimental measurement of the initial tack, peel strength and tack holding ability of the photocurable pressure-sensitive adhesive with a lower hard monomer ratio (THFMA 10) without adding a crosslinking agent are shown in fig. 3, where the initial tack was 12.6N, the 180 ° peel strength was 8.9N/25mm, and the tack holding ability was less than 1h. This indicates that the uncrosslinked linear copolymer has poor cohesive strength, high peel strength and poor permanent tack. After the DAPETA cross-linking agent is added, the peel strength of the pressure-sensitive adhesive (DAPETA-2.5%) obtained when only 2.5% of DAPETA is added is reduced to 8.5N/25mm, and the holding time can reach 6.1h. With the increasing amount of the cross-linking agent, the 10% stripping of DAPETA is reduced to 2.4N/25mm, the holding time exceeds 60h, and the initial adhesion is reduced to the minimum (3.1N).
TABLE 1 composition of various pressure-sensitive adhesives
aDAPETA as a cross-linking agent; bPETA as a cross-linking agent; c, polyether amine modified epoxy acrylate (AgiSyn 703) is used as a cross-linking agent; d bisphenol A epoxy acrylate (RJ 313) as a crosslinker.
Example 2
As shown in example 1, except in the preparation step of the UV light curable solvent-free branched acrylate pressure sensitive adhesive.
Taking THFMA10 as an example, 9g of Lauryl Methacrylate (LMA), 1g of tetrahydrofurfuryl methacrylate (THFMA) and 0.25g of photoinitiator (2-hydroxy-2-methyl-1-phenyl acetone) were mixed and added to a round bottom flask with a stirring device, after purging with nitrogen for 20min, the light intensity was 0.02mW/cm -2 The UV LED light source of (1) was irradiated from the bottom of the round-bottomed flask to initiate monomer polymerization for a certain time (0, 3min,5min,10min, 15min), and the chemical structure and viscosity of the prepolymer at different times (0, 3min,6min,9min,12min,15min,18min, and 21min) were tested by in-situ FTIR and viscometer, respectively.
FIG. 4 is an infrared spectrum of a pressure sensitive adhesive prepolymer at different UV cure times.
FIG. 5 is a graph of pressure sensitive adhesive precursor UV cure time, double bond conversion and viscosity.
1730cm as shown in the figure -1 The absorption peak is C = O stretching vibration peak in acrylic ester monomer and is 1239cm -1 And 1149cm -1 The absorption peak is C-O absorption peak, 2925cm -1 In the side chain corresponding to the LMA unit in the copolymer-CH 2 Absorption peak of expansion vibration, 1081cm -1 The absorption peak is five in the THFMA unitThe telescopic vibration absorption peak of C-O-C in the meta-ring is 1636cm -1 C = C is a double bond absorption peak, the intensity of the double bond absorption peak is gradually reduced after the irradiation of the ultraviolet LED lamp, as can be seen from a relation graph (figure 5) of the UV curing time, the double bond conversion rate and the viscosity, the viscosity of the prepolymer is also continuously improved along with the gradual polymerization of the double bonds in the reaction, after the irradiation of the ultraviolet lamp for 15min, the double bond conversion rate in the prepolymer reaches 61.2 percent, the viscosity is more than 960mPa · s, the process range of the pressure sensitive adhesive coating is basically reached, the surface of the pressure sensitive adhesive tape obtained through further photocuring is uniform, and 1636cm is obtained -1 The C = C double bond absorption peak disappeared, indicating that the reaction was completely proceeding.
Example 3
As shown in example 1, except that in the preparation step of the UV light curable solvent-free branched acrylate pressure sensitive adhesive, further comparison was made with unmodified pentaerythritol triacrylate (PETA), as shown in table 1.
Mixing 1g pentaerythritol triacrylate, 9g lauryl methacrylate, 1g tetrahydrofurfuryl methacrylate and 0.25g photoinitiator (2-hydroxy-2-methyl-1-phenylpropanone), adding into a round bottom flask with a stirring device, purging with nitrogen for 20min, and measuring with 0.02mW/cm light intensity -2 The UV LED light source irradiates from the bottom of the round-bottom flask to initiate monomer polymerization for 15min to obtain a pressure-sensitive adhesive prepolymer for subsequent pressure-sensitive adhesive tape experiments.
Coating the pressure-sensitive adhesive precursor polymer obtained in the step on a polyethylene terephthalate film, and continuously keeping the light intensity at 80mW cm -2 And (3) irradiating the adhesive tape for 5min by a photocuring machine until double bonds are completely converted to obtain the UV photocuring solvent-free branched acrylate pressure-sensitive adhesive tape with the adhesive layer thickness of 25 mu m.
Among these, as shown in fig. 3, when 10% petroleum-based PETA was added, the peel strength was comparable to DAPETA, but the tack-holding performance was inferior. The fact that DAPETA is used as a cross-linking agent after rosin modification has the effect of serving as a tackifying resin while the cohesive force is improved is shown.
Example 4
As shown in example 1, except that in the preparation step of the UV light curable solvent-free branched acrylate pressure sensitive adhesive, further comparison was made with commercial amine modified epoxy acrylate (AgiSyn 703) and bisphenol a acrylate copolymer (RJ 313).
As shown in table 1, pressure sensitive adhesive prepolymers using DAPETA, agiSyn703 and RJ313 as crosslinking agents were prepared, respectively. Taking DAPETA2.5% as an example, 0.25g of abietyl pentaerythritol triacrylate, 9g of lauryl methacrylate, 1g of tetrahydrofurfuryl methacrylate and 0.25g of photoinitiator (2-hydroxy-2-methyl-1-phenylpropanone) were mixed and introduced into a round-bottomed flask with stirring, purged with nitrogen for 20min and then irradiated with light at a intensity of 0.02mW/cm -2 The UV LED light source irradiates from the bottom of the round-bottom flask to initiate monomer polymerization for 15min to obtain a pressure-sensitive adhesive prepolymer for subsequent pressure-sensitive adhesive tape experiments.
Coating the pressure-sensitive adhesive precursor polymer obtained in the step on a polyethylene terephthalate film, and continuously keeping the light intensity at 80mW cm -2 And (3) irradiating the adhesive tape for 5min by a photocuring machine until double bonds are completely converted to obtain the UV photocuring solvent-free branched acrylate pressure-sensitive adhesive tape with the adhesive layer thickness of 25 mu m.
As shown in FIG. 6, in the case of 5% of the added amount, the initial tack and the permanent tack of the photo-curing pressure-sensitive adhesive obtained by crosslinking AgiSyn703 can be 3.1N and 15.3h respectively, which indicates that the photo-curing pressure-sensitive adhesive has a certain cohesive force but low viscosity. The initial adhesion and the permanent adhesion of the photo-curing pressure-sensitive adhesive obtained by using RJ313 as a cross-linking agent are respectively 12.9N and 0.4h, and interfacial damage occurs during glass test, which shows that the pressure-sensitive adhesive has poor cohesion. And the DAPETA is used as a cross-linking agent, so that the initial adhesion (7.2N), the cohesion (the 180-degree peel strength is 5.4N/25 mm) and the permanent adhesion performance (the permanent adhesion time is more than 24 h) of the photo-curing pressure-sensitive adhesive can be effectively balanced.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalents or equivalent changes fall within the protection scope of the present invention.
Claims (10)
1. The rosin-based crosslinking agent is rosinyl pentaerythritol triacrylate, and is characterized in that the structural formula is as follows:
2. the crosslinking agent according to claim 1, wherein the preparation method of the abietyl pentaerythritol triacrylate comprises the following steps:
a1, reacting rosin and oxalyl chloride in a good solvent to obtain rosin acyl chloride;
and A2, dripping a solution containing pentaerythritol triacrylate, an acid-binding agent and a polymerization inhibitor in a certain molar ratio into rosin acyl chloride for esterification reaction to obtain the abietyl pentaerythritol triacrylate.
3. The crosslinking agent according to claim 2, wherein the molar ratio of rosin to oxalyl chloride in step A1 is 1:1 to 2; the reaction temperature is 0-40 ℃, and the reaction time is 1-8 h;
the good solvent is one of dichloromethane, tetrahydrofuran and ethyl acetate.
4. The crosslinking agent according to claim 2, wherein the molar ratio of rosin acyl chloride, pentaerythritol triacrylate, acid scavenger and polymerization inhibitor in step A2 is 1:1: 1.2-1.5: 0.01 to 0.05; the esterification reaction temperature is 20-50 ℃, and the reaction time is 4-12 h;
the acid-binding agent is any one of 4-dimethylamino pyridine, triethylamine, pyridine and sodium bicarbonate;
the polymerization inhibitor is any one of hydroquinone, p-hydroxyanisole and p-benzoquinone;
the solution is any one of dichloromethane, tetrahydrofuran, ethyl acetate, toluene and N, N-dimethylformamide.
5. The crosslinking agent according to claim 1, wherein the crosslinking agent is used for the preparation of colloids.
6. The UV photocuring solvent-free branched acrylate pressure-sensitive adhesive is characterized by comprising the following steps:
b1, adding a certain mass of acrylate soft monomer, acrylate hard monomer and photoinitiator into the cross-linking agent of claim 1, mixing, stirring, purging with nitrogen, irradiating with ultraviolet light to initiate monomer polymerization, and reacting for a certain time to obtain a pressure-sensitive adhesive prepolymer;
and B2, coating the pressure-sensitive adhesive prepolymer on a polyethylene terephthalate film, and carrying out ultraviolet curing to obtain the UV light-cured solvent-free branched acrylate pressure-sensitive adhesive tape.
7. The pressure-sensitive adhesive according to claim 6, wherein the mass ratio of the acrylate hard monomer, the soft monomer, the abietyl pentaerythritol triacrylate and the photoinitiator in the step B1 is 1:1 to 9:0.25 to 1:0.25 to 1;
the acrylate soft monomer is lauryl methacrylate;
the acrylate hard monomer is any one of tetrahydrofurfuryl methacrylate, butyl methacrylate and isobornyl acrylate;
the photoinitiator is any one of xylene ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
8. The pressure-sensitive adhesive according to claim 6, wherein the mixing and stirring in step B1 is carried out in a transparent bottle, and ultraviolet light is irradiated from the bottom of the transparent bottle;
the nitrogen purging time is 20min, and the ultraviolet light intensity is 0.02mW cm -2 The reaction temperature is room temperature, and the reaction time is 5-30 min.
9. The pressure-sensitive adhesive of claim 6, wherein the UV curing in step B2The chemical illumination intensity is 50-100 mW cm -2 The illumination time is 3-10 min.
10. The pressure-sensitive adhesive according to claim 6, wherein the adhesive tape has a layer thickness of 10 to 100 μm.
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