CN116162196A - Light-color high-stability hydrogenated terpene phenol styrene resin and preparation method and application thereof - Google Patents
Light-color high-stability hydrogenated terpene phenol styrene resin and preparation method and application thereof Download PDFInfo
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- CN116162196A CN116162196A CN202211675161.1A CN202211675161A CN116162196A CN 116162196 A CN116162196 A CN 116162196A CN 202211675161 A CN202211675161 A CN 202211675161A CN 116162196 A CN116162196 A CN 116162196A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F8/04—Reduction, e.g. hydrogenation
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Abstract
A light-colored high stability hydrogenated terpene phenol styrene resin made from alpha-pinene, phenol, styrene or a styrene derivative; the alpha-pinene, phenol, styrene or styrene derivative accounts for 1-20% of the total mass of the raw materials, and 1-20% and 60-98% of the total mass of the raw materials; also provided are partial structural formulas and preparation methods of the hydrogenated terpene phenol styrene resin. The resin provided by the invention has the advantages of light color, high stability, good solubility and strong tackifying property, reduces cost, has light color, high stability, wide solubility and strong tackifying property, and can be widely applied to the field.
Description
Technical Field
The invention relates to a light-colored high-stability hydrogenated terpene phenol styrene resin, belongs to the technical field of rubber industry, and particularly belongs to the technical field of preparation of hydrogenated terpene phenol styrene resin. The invention also relates to a light-colored high-stability hydrogenated terpene phenol styrene resin, and a preparation method and application thereof.
Background
Resins are generally organic polymers which have a softening or melting range after heating, tend to flow under external forces during softening, have an indefinite relative molecular weight but are generally high, and are solid, medium-solid, or pseudo-solid at ordinary temperatures, and may be liquid. Has a softening or melting temperature range, tends to flow under external force, and breaks often in the form of shells. In a broad sense, any polymeric compound that can be used as a raw material for processing plastic articles is referred to as a resin, and in a broad sense, a polymer or prepolymer that is used as a plastic substrate. Is generally insoluble in water and soluble in organic solvents.
The terpene resin is prepared from natural turpentine, has the advantages of transparency, no toxicity, neutrality, electric insulation, hydrophobicity, no crystallization, dilute acid and alkali resistance, heat resistance, light resistance, aging resistance, strong adhesion and the like, has good compatibility to various synthetic substances, and is easy to dissolve in aromatic hydrocarbon and vegetable oil. The terpene resin is a thermoplastic block copolymer, has the advantages of light color, low odor, high hardness, high adhesive force, good oxidation resistance, good thermal stability, good compatibility and solubility and the like, and particularly has excellent compatibility, weather resistance and tackifying effect in hot-melt adhesives such as EVA series SS series, S S series and the like. The product is widely applied to the aspects of adhesives, double-sided adhesive tapes, solvent-based glues, book binding plates, color-mounting, adhesive tapes, olefin adhesive tapes, kraft paper adhesive tapes, adhesive tape labels, woodworking glues, pressure-sensitive adhesives, thermosol, sealant, paint, printing ink, other polymer modifying agents and the like.
In the fields of adhesives and coatings, terpene resins are widely used as a very excellent tackifier, and are added in a large amount in pressure-sensitive adhesives because of their good initial tackiness and peel strength. However, the terpene resin is generally polymerized by one or more of alpha-pinene, beta-pinene, limonene and the like which are main components of turpentine, along with the rising of the price of turpentine, the production cost of the terpene resin is increased, and the application of the terpene resin is influenced, so that a series of modified terpene resins are generated, wherein the most common terpene resins are introduced for modification, so that the copolymer terpene-styrene resin is obtained, the cost is reduced, the color and luster are water white and transparent, the thermal stability is better, the solubility in aromatic compounds is obviously better than that of the terpene resin, and the tackifying effect is greatly reduced compared with that of the terpene resin.
The terpene-phenol resin can improve the compatibility with a plurality of natural and synthetic polymers, contains a hydroxyl structural unit, has better viscosity when the hydroxyl value is proper, but has darker color, and other auxiliary agents such as a light-color additive, an antioxidant and the like are often required to be added, so that the wide application of the terpene-phenol resin is limited; terpene-alpha-methyl styrene has excellent heat resistance and mechanical strength, good appearance, bright surface and transparent color, and in addition, alpha-methyl styrene is an important byproduct in the industrial cumene method for producing phenol, and phenol and alpha-methyl styrene have common industrial advantages in the prior art, but have poor tackifying effect as the terpene-styrene resin.
At present, no resin with simple and easily obtained raw materials, lower production cost, better color, stability, viscosity, compatibility and the like is found. Therefore, it is important to develop a resin with low cost, light color, high stability, good compatibility, good solubility and strong tackifying property.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides light-colored high-stability hydrogenated terpene phenolic styrene resin and a preparation method thereof, which are characterized in that alpha-pinene, phenol, styrene or a styrene derivative (alpha-methylstyrene and p-methylstyrene) is subjected to multi-copolymerization, then is highly hydrogenated, and the production cost is reduced.
An object of the present invention is to provide a resin which is low in cost.
The second purpose of the invention is to develop a resin with light color, high stability, good solubility and strong tackifying property, so as to be expected to reduce the cost and simultaneously endow the product with the characteristics of light color, high stability, wide solubility, excellent tackifying property and the like, thereby obtaining the light-color high-stability hydrogenated terpene phenol styrene resin with good appearance and performance.
In order to solve the technical problems, the invention is realized by the following technical scheme:
in one aspect, the present invention provides a light colored high stability hydrogenated terpene phenol styrene resin and provides some structural formulas of the hydrogenated terpene phenol styrene resin.
A second aspect of the present invention is to provide a formulation of the light-colored high stability hydrogenated terpene phenolic styrene resin of the first aspect of the present invention, said hydrogenated terpene phenolic styrene resin being made of α -pinene, phenol, styrene or a styrene derivative; the alpha-pinene, phenol, styrene or styrene derivative accounts for 1-20% of the total mass of the raw materials, and 1-20% and 60-98% of the total mass of the raw materials; preferably 5 to 15%, 65 to 95%; more preferably 10 to 15%, 70 to 85%; more preferably 8 to 13%, 75 to 85%.
Further, as a more preferred embodiment of the present invention, the styrene derivative is one or both of alpha-methylstyrene and para-methylstyrene.
Further, as a more preferred embodiment of the present invention, the resin has a softening point of 60℃to 140℃and a color of < 1, an acid value of < 1.0mgKOH/g and an iodine value of < 3.0g/100g.
A third aspect of the present invention is to provide the method for producing a hydrogenated terpene phenol styrene resin according to the first or second aspect, wherein the method for producing a hydrogenated terpene phenol styrene resin having a light color and high stability comprises:
mixing the raw materials with a solvent to obtain a mixture;
a polymerization reaction step, namely adding a polymerization reaction catalyst into the mixture, and enabling the mixture to undergo multi-polymerization reaction through cationic polymerization under the action of the polymerization reaction catalyst to obtain a polymerization solution;
a hydrogenation reaction step, namely washing the polymerization liquid with water, separating the liquid, and adding a hydrogenation reaction catalyst to carry out hydrogenation reaction to obtain a mixed organic liquid;
filtering, washing and separating the mixed organic liquid, and then carrying out reduced pressure distillation to obtain the light-color high-stability hydrogenated terpene phenol styrene resin.
Further, as a more preferred embodiment of the present invention, the polymerization catalyst is selected from AlCl 3 、 F 3 C 3 C 3 、F 3 C 25 OC 25 、SbCl 3 、ZnCl 2 One or more of the following.
The polymerization catalyst is a Lewis acid commonly used in cationic polymerization, and forms a complex ion pair with a proton donor (trace water in air) through the Lewis acid to trigger a monomer, and the generated carbocation active species and counter ions are triggered to form an ion pair, so that monomer molecules are continuously inserted into the complex ion pair for growth.
Further, as a more preferable embodiment of the present invention, the polymerization catalyst is added in an amount of 1% to 7% by mass of the total mass of the raw materials. Preferably 2% to 6%, more preferably 3% to 4%.
Further, as a more preferred embodiment of the present invention, the hydrogenation catalyst is selected from Pd/C, zrCl 4 、BiCl 3 One or more of NiThe addition amount of the hydrogenation catalyst is 0.5-10% of the total mass of the raw materials. Preferably 2% -8%; more preferably 3% to 7%; more preferably 4 to 6%.
When the hydrogenation catalyst is multiple, the dosage of each substance is 0-10% of the total mass of the raw materials, and Pd/C, zrCl 4 、iCl 3 Ni cannot be all zero. The hydrogenation catalyst enriches hydrogen thereon in the form of atoms or free radicals to react with unsaturated bonds.
Further, as a more preferred embodiment of the present invention, chain transfer may be limited considering factory practice and low temperature of cationic polymerization, the temperature of the multi-polymerization is-20 to 50℃and the total reaction time is 8 to 12 hours. Preferably, the temperature is between-10 and 40 ℃, and the total reaction time is between 8.5 and 11.5 hours; more preferably, the temperature is between-15 and 30 ℃ and the total reaction time is between 9 and 11 hours; more preferably at a temperature of-5 to 20℃and a total reaction time of 9.5 to 10.5 hours.
Further, as a more preferred embodiment of the present invention, the hydrogenation reaction is carried out at a temperature of 150 to 250℃and a hydrogen pressure of 10 to 25MPa for a total reaction time of 2 to 10 hours.
Preferably, the hydrogenation temperature is too high to crack easily, and the hydrogenation reaction temperature is 200-250 ℃, the hydrogen pressure is 10-25 MPa, and the total reaction time is 2-8 h in consideration of actual and reduced cracking of a factory. Preferably, the temperature is 210-240 ℃, the hydrogen pressure is 15-20 MPa, and the total reaction time is 3-7 h; more preferably, the temperature is 220-230 ℃, the hydrogen pressure is 16-20 MPa, and the total reaction time is 4-6 h.
Further, as a more preferred embodiment of the present invention, the boiling point of the mixed solvent of the present application is 150 or less, so that the distillation temperature is required to be more than 150 ℃. Preferably, the reduced pressure distillation is at a temperature of 160 to 200 ℃ in consideration of the boiling point of the solvent and reduction of the influence on the product properties, since the distillation temperature is too high to be easily cracked. Preferably 170-190 ℃; more preferably 175 to 185 ℃.
Further, as a more preferred embodiment of the present invention, the solvent is selected from one or more of toluene, cyclohexane, petroleum ether, chloroform. The addition amount of the solvent is 50% -200% of the total mass of the raw materials. Preferably 50% -150%; more preferably 100% to 120%.
Further, as a more preferred embodiment of the present invention, a process for preparing a light-colored high-stability hydrogenated terpene-phenol-styrene resin, comprising the steps of:
(1) Adding raw materials, a solvent and a polymerization catalyst into a reactor according to a mass ratio, and performing multi-polymerization reaction to obtain a polymerization solution;
(2) Washing and separating the polymerization liquid, adding an organic phase and a hydrogenation catalyst into a reaction kettle, and carrying out hydrogenation reaction to obtain a mixed organic liquid;
(3) Filtering, washing and separating the mixed organic liquid, and then distilling under reduced pressure to obtain the light-color high-stability hydrogenated terpene phenol styrene resin.
A fourth aspect of the present invention is to provide the use of the hydrogenated terpene phenol styrene resin according to the first, second and third aspects, a light-colored high-stability hydrogenated terpene phenol styrene resin according to the above, which is used in the fields of adhesives and paints.
The properties of the products according to the invention are determined by the softening point (ring and ball method), the colour (iron-cobalt method), the acid number (mgO/g).
Compared with the prior art, the invention has the following beneficial effects:
1. the light-colored high-stability hydrogenated terpene phenol styrene resin has lighter color and luster than the terpene resin widely used at present, so that the hydrogenated terpene phenol styrene resin can be applied to more fields.
2. The light-colored high-stability hydrogenated terpene phenol styrene resin has high stability, and the stability is higher than that of the terpene resin widely used at present, so that the hydrogenated terpene phenol styrene resin can be applied to more fields.
3. The light-colored high-stability hydrogenated terpene phenol styrene resin of the invention has good compatibility with the main stream thermoplastic elastomer, so the hydrogenated terpene phenol styrene resin can be used as tackifying resin in the adhesive field represented by pressure sensitive adhesives.
4. The hydrogenated terpene phenol styrene resin of the invention can be compatible with main stream solvents such as toluene, cyclohexane, n-hexane, ethyl acetate and the like, can be mutually soluble with various solvents such as aromatic hydrocarbon, naphthene, aliphatic hydrocarbon and the like, and has good tackifying effect, so the hydrogenated terpene phenol styrene resin can be applied to the fields of adhesives and coatings.
5. In the raw materials used for the light-colored high-stability hydrogenated terpene phenol styrene resin, phenol, styrene and derivatives thereof are chemical products with low price, the price of actual industrial production raw materials is correspondingly lower, the commodity price is close to the raw material cost due to marginal cost effect after industrialization, compared with the existing resins such as terpene resin with expensive raw materials, the raw materials have the advantage of lower production cost, and the hydrogenated terpene phenol styrene resin has the characteristics of light color, high stability and the like, so the hydrogenated terpene phenol styrene resin is suitable for being applied in a plurality of fields and popularization and application.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a hydrogenated terpene phenol styrene resin prepared in preparation example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the hydrogenated terpene phenol styrene resin prepared in preparation example 1 of the present invention;
FIG. 3 is a GPC chromatogram of the hydrogenated terpene phenol styrene resin obtained in production example 1 of the present invention.
Detailed Description
In order to better understand the technical solutions in the present application, the following description will clearly and completely describe the technical solutions in the embodiments of the present application in conjunction with the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments, and do not limit the protection scope of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure. Any modifications, equivalent substitutions, etc. which are within the spirit and scope of the present invention should be included in the scope of the present invention.
In the description of the present application, the meaning of "plurality" is two or more, unless explicitly defined otherwise.
In the fields of adhesives and coatings, the production cost of terpene resins is greatly limited by the increase of the price of turpentine. The terpene-styrene resin has low cost, white and transparent color, better thermal stability and better solubility in aromatic compounds than terpene resin, but the tackifying effect is greatly reduced compared with terpene resin. Terpene-phenol resins, although compatible and tacky, are darker in color and therefore limited in use. Terpene-alpha-methylstyrene has good heat resistance and transparent color, but poor adhesion. At present, no resin with simple and easily obtained raw materials, lower production cost, better color, stability, viscosity, compatibility and other properties is found in the market. Therefore, it is important to develop a resin with low cost, light color, high stability, good compatibility, good solubility and strong tackifying property.
The first aspect of the present invention is to provide a light-colored high-stability hydrogenated terpene phenol styrene resin having a structural formula comprising:
wherein each structural formula comprises R 1 、R 2 、R 3 、R 4 One or more of the structures, and R in the structural formula 1 、R 2 、R 3 、R 4 The arrangement order is interchangeable and is not limited to the structural formulae given above;
r in the structural formula 1 The structure is as follows:
R 2 the structure is as follows:
R 3 the structure is as follows:
R 4 the structure is as follows:
at R 1 、R 2 、R 3 、R 4 In the structure, 1 is less than n 1 +n 2 +n 3 +n 4 ＜30。
For further understanding and practicing the present technical solution by those of ordinary skill in the art, the structural formula of the hydrogenated terpene phenol styrene resin further comprises:
for further understanding and practicing the present invention by those of ordinary skill in the art, a second aspect of the present invention is to provide a formulation of a light colored high stability hydrogenated terpene phenolic styrene resin made from alpha-pinene, phenol, styrene or a styrene derivative.
The existing terpene resin is light in color and high in stability, but is generally polymerized by one or more of alpha-pinene, beta-pinene, limonene and the like which are main components of turpentine, and the production cost of the terpene resin is increased along with the large price rise of turpentine, so that the application of the terpene resin is influenced. Thus, in the present invention, a hydrogenated terpene phenol styrene resin having low raw material cost is provided. The prices of the various raw materials according to the present invention are shown in Table 1 below.
TABLE 1 raw material prices approximately interval
| Raw materials | Price of |
| Styrene, technical grade | 0.7-0.9 ten thousand yuan/ton |
| Alpha-methyl styrene, technical grade | 1.2-1.6 ten thousand yuan/ton |
| Para-methylstyrene, technical grade | 2-2.5 ten thousand yuan/ton |
| Phenol, technical grade | 0.7-0.9 ten thousand yuan/ton |
| Alpha-pinene, technical grade | 6-8 ten thousand yuan/ton |
In the prior art, the compatibility and viscosity of the terpene-phenol resin are good, but the color of the terpene-phenol resin is quite dark, so that the application of the terpene-phenol resin in a plurality of fields is limited. While terpene-alpha-methylstyrene has excellent heat resistance and mechanical strength, is easy to see, has bright surface and transparent color, and is an important byproduct in the industrial cumene method for producing phenol, phenol and alpha-methylstyrene have common industrial advantages, but have poor tackifying effect as terpene-styrene resin and limit the application of the terpene-alpha-methylstyrene in a plurality of fields.
As the invention adopts the raw materials with high price as far as possible, the price of the alpha-pinene is higher as shown in the table 1, if the using amount of the alpha-pinene in the raw materials is too high, the whole production cost of the resin is increased, but the simple combination and stacking of the raw materials can not necessarily achieve the desired technical effect, and the performance of the product can not meet the requirements without using the alpha-pinene in consideration of the performance problem of the product. In order to solve the problem, the inventor researches out a scientific and reasonable material ratio under the condition of ensuring the low production cost of the resin.
In order to be more easily understood and implemented by the person of ordinary skill in the art, the inventor determines the feeding ratio of the raw materials of the hydrogenated terpene phenol styrene resin according to the intensive study on a large amount of experimental basis and years of study, and the invention also provides the specific proportion of the raw materials of the hydrogenated terpene phenol styrene resin: the alpha-pinene, phenol, styrene or styrene derivative accounts for 1-20% of the total mass of the raw materials, 1-20% and 60-98% of the total mass of the raw materials. And the softening point of the resin is 60-140 ℃, the color and luster is less than 1, the acid value is less than 1.0mgKOH/g, and the iodine value is less than 3.0g/100g.
For further understanding and implementing the technical scheme by those of ordinary skill in the art, the styrene derivative is one or two of alpha-methyl styrene and p-methyl styrene.
The cationic polymerization belongs to fast initiation and fast growth, and the application uses Lewis acid commonly used in cationic polymerization as a polymerization reaction catalyst, forms a complex ion pair with a proton donor (trace water in air) through the Lewis acid, initiates a monomer, initiates generated carbocationic active species and counter ions to form an ion pair, continuously inserts and grows monomer molecules, and then enriches hydrogen on the monomer molecules in an atomic form or a free radical form to act with unsaturated bonds under the action of a hydrogenation reaction catalyst. Taking a synthetic hydrogenated polystyrene resin as an example, alCl is first used 3 Forming complex ion pair with water to trigger styrene in original styreneDouble bond site formation of carbocationic species and AlCl 3 And forming a complex anion pair by water, continuously inserting a styrene monomer into the complex anion pair to quickly form a high molecular long chain, carrying out chain transfer and chain termination, completing a polymerization reaction, enriching hydrogen on Pd/C under the conditions of high temperature and high pressure in a hydrogenation reaction, and reacting the hydrogen with benzene ring big pi bonds and other unsaturated bonds on polystyrene in an atomic form or in a free radical form until the saturated hydrogenated polystyrene is basically formed under the temperature and the pressure, thus obtaining a final product, namely hydrogenated polystyrene resin.
It should be noted that the structural formula of the hydrogenated terpene phenol styrene resin is not only the mode disclosed in the application, but also the resins with other structural formulas prepared by adopting the formula and the preparation method disclosed in the application are also within the scope of protection of the application.
Comparative example 1
A method for preparing unhydrogenated terpene phenol styrene resin, comprising the steps of:
(1) 300g of toluene, 400g of cyclohexane and 7g of AlCl are reacted at-20 DEG C 3 、7g ZnCl 2 Adding the mixture into a reactor, and stirring to cool the reaction system to-20 ℃;
(2) Respectively weighing 18g, 60g, 300g and 300g of alpha-pinene, phenol, styrene and alpha-methylstyrene, and then adding the four raw materials into the reaction system of the step (1), and finishing the reaction after 9h for 58min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, separating the solution, transferring the solution into a reduced pressure distillation container, heating the solution in an oil bath for reduced pressure distillation, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating the solution to 200 ℃, continuously distilling the solution for 60 minutes at the temperature, and pouring out the product while the solution is hot to obtain the unhydrogenated terpene phenol styrene resin.
The product of this preparation example was cooled and weighed to give a product weight of 523.61g, a yield of 77.23%, a softening point of 111.5 ℃, a color number=6, and an acid value of 0.88mgKOH/g.
Preparation example 1
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 300g of toluene, 400g of cyclohexane, 7g of AlCl3 and 7g of ZnCl2 are added into a reactor at the temperature of minus 20 ℃ and stirred to cool the reaction system to the temperature of minus 20 ℃;
(2) Respectively weighing 18g, 60g, 300g and 300g of alpha-pinene, phenol, styrene and alpha-methylstyrene, and then adding the four raw materials into the reaction system of the step (1), and finishing the reaction after 9h for 58min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, adding an organic phase into a reaction kettle after liquid separation, respectively adding 6g, 18g and 12g of ZrCl4, biCl3 and Ni catalysts, then introducing hydrogen with the pressure of 20MPa, heating to 240 ℃, maintaining for 10 hours, filtering, discharging, washing with water, and separating to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 200 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation example was cooled and weighed to give a product weight of 513.31g, a yield of 75.71%, a softening point of 125 ℃, a color number of < 1, and an acid value of 0.22mgKOH/g.
1. Performance testing
1. Molecular weight analysis
The hydrogenated terpene phenol styrene resin obtained in preparation example 1 was analyzed for molecular weight, and the results are shown in Table 2.
TABLE 2 molecular weight case
| Distribution name | M n | M w | MP | M z | M z+1 | Polydispersities (polydispersities) |
| Data | 1357g/mol | 5907g/mol | 5012g/mol | 14206g/mol | 22978g/mol | 4.35 |
2. Thermal stability
The hydrogenated terpene phenol styrene resin obtained in preparation example 1 was subjected to thermal stability comparison between the existing commercial terpene resin T-100 and the unhydrogenated terpene phenol styrene resin obtained in comparative example 1, and the commercial terpene resin T-100, the unhydrogenated terpene phenol styrene resin and the hydrogenated terpene phenol styrene resin were treated at 180℃for 8 hours, respectively, and the results before and after the comparison are shown in Table 3 below.
TABLE 3 thermal stability vs. case
As the greater the color change before and after the high temperature treatment of the resin, the worse the stability, it is seen from Table 3 that the hydrogenated terpene phenol styrene resin prepared in the present application has better thermal stability than the commercial terpene resin T-100 and also better stability than the unhydrogenated terpene phenol styrene resin.
3. Solubility of
4 parts of the hydrogenated terpene phenol styrene resin prepared in preparation example 1 with equal mass are weighed and placed in four solvents of toluene, cyclohexane, normal hexane and ethyl acetate respectively, the mass ratio of the solvent to the hydrogenated terpene phenol styrene resin is 1:1, the dissolution condition is observed, and the experimental results are shown in the following table 4.
TABLE 4 dissolution of hydrogenated terpene phenol styrene resins in different solvents
| Solvent(s) | Dissolution conditions |
| Toluene (toluene) | Dissolving |
| Cyclohexane | Dissolving |
| N-hexane | Dissolving |
| Acetic acid ethyl ester | Dissolving |
Because the ethyl acetate has low toxicity, the ethyl acetate is used as a solvent by most adhesives, and the hydrogenated terpene phenol styrene resin prepared by the method can be dissolved in the ethyl acetate and can be also dissolved in common aromatic hydrocarbon (represented by toluene), cycloparaffin (represented by cyclohexane) and aliphatic hydrocarbon (n-hexane), so that the hydrogenated terpene phenol styrene resin is suitable for a wider scene, can be applied in more fields and has wide application fields.
4. Characterization analysis
For preparation ofThe hydrogenated terpene phenol styrene resin obtained in example 1 was subjected to performance analysis 1 The H-NMR spectrum is shown in FIG. 1, which shows 13 The C-NMR spectrum is shown in FIG. 2, and the GPC chromatogram thereof is shown in FIG. 3.
Preparation example 2
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 100g of toluene, 20g of chloroform and 3.5g of BF were reacted at-20 DEG C 3 ·C 2 H 5 OC 2 H 5 Adding the mixture into a reactor, and stirring to cool the reaction system to-20 ℃;
(2) Respectively weighing 3g, 10g, 50g and 50g of alpha-pinene, phenol, alpha-methylstyrene and p-methylstyrene raw materials, then adding the materials into the reaction system of the step (1), and finishing the reaction after 8h and 16min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, separating the solution, adding an organic phase into a reaction kettle, and respectively adding ZrCl 4 、BiCl 3 2g and 4g of each catalyst, then introducing hydrogen with the pressure of 15MPa, heating to 210 ℃, maintaining for 8 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 180 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation example was cooled and weighed to give a product weight of 108.74g, a yield of 96.23%, a softening point of 80 ℃, a color number of < 1, and an acid value of 0.26mgKOH/g.
Preparation example 3
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 50g of toluene, 50g of cyclohexane, 50g of petroleum ether and 2g of AlCl are added at-20 DEG C 3 、2g F 3 C 3 OC 3 Adding the mixture into a reactor, and stirring to cool the reaction system to-20 ℃;
(2) Respectively weighing 3g, 10g and 100g of alpha-pinene, phenol and p-methylstyrene as raw materials, then adding the raw materials into the reaction system of the step (1), and finishing the reaction after 9h and 18min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, separating the solution, adding an organic phase into a reaction kettle, and respectively adding iCl 3 3g of Ni catalyst and 3g of Ni catalyst respectively, then introducing hydrogen with the pressure of 15MPa, heating to 200 ℃, maintaining for 8 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 200 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation was cooled and weighed to give a product weight of 90.43g, a yield of 80.03%, a softening point of 101 ℃, a color number of < 1, and an acid value of 0.33mgKO/g.
Preparation example 4
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 50g of cyclohexane, 50g of petroleum ether and 2g of AlCl are added at the temperature of minus 20 DEG C 3 、1g SbCl 3 、1g ZnCl 2 Adding the mixture into a reactor, and stirring to cool the reaction system to-20 ℃;
(2) Respectively weighing 3g, 10g and 100g of alpha-pinene, phenol and styrene, then adding the three raw materials into the reaction system of the step (1), and finishing the reaction after 7h and 34in to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, separating the solution, adding an organic phase into a reaction kettle, and respectively adding ZrCl 4 2g and 4g of Ni catalysts, then introducing hydrogen with the pressure of 15MPa, heating to 200 ℃, maintaining for 8 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating and distilling under reduced pressure by an oil bath, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 180 ℃, continuously distilling for 60 minutes at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation was cooled and weighed to give a product weight of 97.86g, a yield of 68.86%, a softening point of 115℃and a color number of < 1, an acid number of 0.21g O/g.
Preparation example 5
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 300g of toluene, 200g of cyclohexane, 100g of petroleum ether, 50g of chloroform and 21g of AlCl at the temperature of minus 20 DEG C 3 Adding the mixture into a reactor, and stirring to cool the reaction system to-20 ℃;
(2) Respectively weighing 30g, 300g, 150g and 150g of alpha-pinene, phenol, styrene, alpha-methylstyrene and p-methylstyrene, and then adding the five raw materials into the reaction system of the step (1), and finishing the reaction after 9h and 40min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, adding an organic phase into a reaction kettle after liquid separation, adding 30g of Pd/C catalyst, then introducing hydrogen with the pressure of 20MPa, heating to 220 ℃, maintaining for 10 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 200 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation was cooled and weighed to give a product weight of 578.69g, a yield of 86.63%, a softening point of 111 ℃, a color number of < 1, and an acid value of 0.43mgKO/g.
Preparation example 6
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 110.0g cyclohexane and 3.5g AlCl3 are added into a reactor at the temperature of minus 10 ℃ and stirred to cool the reaction system to minus 10 ℃;
(2) Respectively weighing 5g, 15g, 85g and 15g of alpha-pinene, phenol, styrene and alpha-methylstyrene raw materials, and then adding the raw materials into the reaction system in the step (1) to react for 8h and 20min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, adding an organic phase into a reaction kettle after liquid separation, adding 5g of Pd/C catalyst, then introducing hydrogen with the pressure of 10MPa, heating to 200 ℃, maintaining for 6 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 200 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation was cooled and weighed to give a product weight of 116.27g, a yield of 98.53%, a softening point of 67 ℃, a color number of < 1 and an acid value of 0.36mgKOH/g.
Preparation example 7
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 300g of cyclohexane, 400g of petroleum ether and 10g of AlCl are added at the temperature of minus 5 DEG C 3 Adding the mixture into a reactor, and stirring to cool the reaction system to-5 ℃;
(2) Respectively weighing 20g, 50g and 500g of alpha-pinene, phenol and styrene, then adding the materials into the reaction system of the step (1), and finishing the reaction after 8h and 23min to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, adding an organic phase into a reaction kettle after liquid separation, respectively adding 10g and 15g of Pd/C, ni catalysts, then introducing hydrogen with the pressure of 15MPa, heating to 220 ℃, maintaining the temperature for 8 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating in an oil bath, distilling under reduced pressure, setting the reduced pressure distillation temperature to 100 ℃, then slowly heating to 200 ℃, continuously distilling for 60min at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation example was cooled and weighed to give a product weight of 526.28g, a yield of 92.33%, a softening point of 102 ℃, a color number of < 1 and an acid value of 0.6mgKOH/g.
Preparation example 8
A preparation method of light-colored high-stability hydrogenated terpene phenol styrene resin comprises the following steps:
(1) 300g of toluene, 300g of cyclohexane, 100g of chloroform, 10g of AlCl are reacted at-10 DEG C 3 、10g SbCl 3 Adding the mixture into a reactor, and stirring to cool the reaction system to-10 ℃;
(2) Respectively weighing 10g, 40g, 300g and 300g of alpha-pinene, phenol, styrene and alpha-methylstyrene, and then adding the materials into the reaction system of the step (1) to react for 9h26in, so as to obtain a polymerization solution;
(3) Washing the polymerization solution obtained in the step (2) to be neutral, separating the solution, adding an organic phase into a reaction kettle, and respectively adding ZrCl 4 、 iCl 3 15g and 15g of two catalysts, then introducing hydrogen with the pressure of 18MPa, heating to 240 ℃, maintaining for 8 hours, filtering, discharging, washing with water, and separating liquid to obtain a semi-finished product;
(4) Transferring the semi-finished product obtained in the step (3) into a reduced pressure distillation container, heating and distilling under reduced pressure by an oil bath, setting the reduced pressure distillation temperature to 100 ℃, then slowly raising the temperature to 200 ℃, continuously distilling for 60 minutes at the temperature, pouring out the product while the product is hot, and obtaining the light-color high-stability hydrogenated terpene phenol styrene resin.
The product of this preparation was cooled and weighed to give a product weight of 561.28g, a yield of 86.35%, a softening point of 109 ℃, a color number of < 1 and an acid value of 0.52g O/g.
Application example 1
A hot melt type thermoplastic elastomer pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 100 parts of SIS (styrene-isoprene-styrene block copolymer), 20 parts of C5 petroleum resin, 80 parts of hydrogenated terpene phenol styrene resin, 40 parts of naphthenic oil, 1 part of zinc N, N-dibutyl dithiocarbamate and 2 parts of 264 anti-aging agent.
A preparation method of a hot melt type thermoplastic elastomer pressure-sensitive adhesive comprises the following steps: weighing SIS (styrene-isoprene-styrene block copolymer), C5 petroleum resin, hydrogenated terpene phenol styrene resin, naphthenic oil, N-dibutyl zinc dithiocarbamate and 264 anti-aging agent according to parts by weight, uniformly mixing, adding into a reaction kettle, heating while slowly stirring, wherein the maximum temperature is not more than 160 ℃, heating and mixing the mixture to form a viscous substance, and discharging to obtain the hot melt type thermoplastic elastomer pressure-sensitive adhesive.
The hot melt type thermoplastic elastomer pressure-sensitive adhesive prepared in application example 1 was tested according to the G4851-84 standard, test results: the holding time of the pressure-sensitive adhesive is more than 24.
Application example 2
A solvent type thermoplastic elastomer pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 100 parts of SIS (styrene-isoprene-styrene block copolymer), 100 parts of hydrogenated terpene phenol styrene resin, 20 parts of C5 petroleum resin, 10 parts of naphthenic oil, 1 part of 264 anti-aging agent, 100 parts of toluene and 230 parts of normal hexane.
A preparation method of a solvent type thermoplastic elastomer pressure-sensitive adhesive comprises the following steps: weighing SIS (styrene-isoprene-styrene block copolymer), hydrogenated terpene phenol styrene resin, C5 petroleum resin, naphthenic oil, 264 anti-aging agent, toluene and normal hexane according to parts by weight, uniformly mixing, adding into a reaction kettle, heating while slowly stirring, heating to a maximum temperature of not more than 30 ℃, heating and mixing the mixture to obtain oily substances, and discharging to obtain the solvent type thermoplastic elastomer pressure-sensitive adhesive.
The solvent type thermoplastic elastomer pressure-sensitive adhesive prepared in application example 1 was tested according to the G4851-84 standard, and the test results: the holding time of the pressure-sensitive adhesive is more than 24 hours.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A light-colored high stability hydrogenated terpene phenolic styrene resin, characterized in that the hydrogenated terpene phenolic styrene resin has a structural formula comprising:
and/or
And/or
And/or
Wherein the structural formula comprises R 1 、R 2 、R 3 、R 4 One or more of the structures, and R in the structural formula 1 、R 2 、R 3 、R 4 The arrangement order is interchangeable; r in the structural formula 1 The structure is as follows:
r in the structural formula 2 The structure is as follows:
r in the structural formula 3 The structure is as follows:
r in the structural formula 4 The structure is as follows:
at R 1 、R 2 、R 3 、R 4 In the structure, 1 is less than n 1 +n 2 +n 3 +n 4 ＜30。
2. A light-colored high stability hydrogenated terpene phenolic styrene resin according to claim 1, wherein: the hydrogenated terpene phenol styrene resin is prepared from alpha-pinene, phenol, styrene or a styrene derivative.
3. The light-colored high-stability hydrogenated terpene phenol styrene resin according to claim 2, characterized in that: the alpha-pinene, phenol, styrene or styrene derivative accounts for 1-20% of the total mass of the raw materials, 1-20% and 60-98% of the total mass of the raw materials.
4. A light-colored high stability hydrogenated terpene phenolic styrene resin according to claim 2 or 3, characterized in that: the styrene derivative is selected from one or two of alpha-methyl styrene and p-methyl styrene.
5. A process for preparing a light colored high stability hydrogenated terpene phenolic styrene resin comprising:
mixing the raw materials with a solvent to obtain a mixture;
a polymerization reaction step, namely adding a polymerization reaction catalyst into the mixture, so that the mixture is subjected to multi-polymerization reaction under the action of the polymerization reaction catalyst to obtain a polymerization solution;
a hydrogenation reaction step, namely washing the polymerization liquid with water, separating the liquid, and adding a hydrogenation reaction catalyst to carry out hydrogenation reaction to obtain a mixed organic liquid;
filtering, washing and separating the mixed organic liquid, and then carrying out reduced pressure distillation to obtain the light-color high-stability hydrogenated terpene phenol styrene resin.
6. The process for preparing a light-colored high-stability hydrogenated terpene-phenol-styrene resin according to claim 5, wherein: the polymerization catalyst is selected from AlCl 3 、BF 3 ·CH 3 OCH 3 、BF 3 ·C 2 H 5 OC 2 H 5 、SbCl 3 、ZnCl 2 One or more of the following; the addition amount of the polymerization catalyst is 1% -7% of the total mass of the raw materials.
7. The process for preparing a light-colored high-stability hydrogenated terpene-phenol-styrene resin according to claim 5, wherein: the hydrogenation catalyst is selected from Pd/C, zrCl 4 、BiCl 3 One or more of Ni, and the addition amount of the hydrogenation catalyst is 0.5-10% of the total mass of the raw materials.
8. The process for preparing a light-colored high-stability hydrogenated terpene-phenol-styrene resin according to claim 5, wherein: the solvent is selected from one or more of toluene, petroleum ether, cyclohexane and chloroform, and the addition amount of the solvent is 50-200% of the total mass of the raw materials.
9. The process for preparing a light-colored high-stability hydrogenated terpene-phenol-styrene resin according to claim 5, wherein: the temperature of the multi-element polymerization reaction is between-20 ℃ and 50 ℃ and the total reaction time is between 8 and 12 hours;
the temperature of the hydrogenation reaction is 150-250 ℃, the hydrogen pressure is 10-25 MPa, and the total reaction time is 2-10 h;
the temperature of the reduced pressure distillation is 160-200 ℃.
10. Use of a light-colored high-stability hydrogenated terpene-phenol-styrene resin according to any of the claims 1-4, characterized in that: the hydrogenated terpene phenol styrene resin is applied to the fields of adhesives and coatings.
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