CN116178735A - Synthesis of hydrocarbon petroleum resin modified silicone resin - Google Patents
Synthesis of hydrocarbon petroleum resin modified silicone resin Download PDFInfo
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- CN116178735A CN116178735A CN202310075496.8A CN202310075496A CN116178735A CN 116178735 A CN116178735 A CN 116178735A CN 202310075496 A CN202310075496 A CN 202310075496A CN 116178735 A CN116178735 A CN 116178735A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract
The invention is suitable for the field of compound synthesis, and provides a synthesis method of hydrocarbon petroleum resin modified silicone resin. Aims at solving the technical problems that the silicon resin in the prior art has defects in curing, adhesion, solvent resistance, mechanical strength and the like, thereby limiting the application range.
Description
Technical Field
The invention belongs to the field of compound synthesis, and particularly relates to synthesis of hydrocarbon petroleum resin modified silicone resin.
Background
Organosilicon compounds are compounds containing Si-C bonds and Si-O-Si bonds, and those compounds which are linked to silicon atoms via organic groups, such as oxygen, sulfur, nitrogen, etc., are also customarily referred to as organosilicon compounds. The organic silicon resin, namely the polyorganosiloxane, is a polymer which contains Si-O-Si chains and is at least linked with one organic group ([ -RSiR '-O ]; R, R' is alkyl or aryl) on the silicon atom to form a main chain. The linear polysiloxanes contain approximately thousands of [ -RSiR' -O ] units, known as silicone rubbers. The end-capped linear polysiloxane with less than 1000 [ -RSiR' -O ] units is oily fluid (silicone oil), the polyorganosiloxane with high cross-linked network structure, si-O bond as main molecular chain and organosilicon polymer with high branching degree is organosilicon resin, also called silicone resin.
The organic silicon resin is an important component of an organic silicon polymer, and Si-O-Si is taken as a main chain, and an organic group is linked on a silicon atom. A semi-inorganic polymer with high cross-linking function is prepared through hydrolyzing the organosilane with multi-functional groups to obtain the prepolymer of silicon resin, and cross-linking the prepolymer to become insoluble solid silicon resin with three-dimensional network structure. It may be a homopolymer of one monomer or a copolymer of a plurality of monomers.
There are various classification methods for silicone resins. The main chain structure is divided into pure silicone resin and modified silicone resin, the former is a typical polysiloxane structure, and the former can be further divided into methyl silicone resin, phenyl silicone resin, methyl phenyl silicone resin and the like according to the types of organic substituents connected on silicon atoms; the modified silicone resin is a thermoset polysiloxane hybridized with an organic resin, or a polysiloxane modified with other siloxanes and carbon functional silanes.
The silicon resin belongs to thermosetting plastics, the most outstanding performance is excellent thermal oxidation stability, the mass loss rate of the silicon resin is lower than 20% after the silicon resin is heated for 24 hours at 350 ℃, and the mass loss rate of general organic resin reaches 70% -90%; another outstanding property of silicone resins is excellent electrical insulation, an electrical strength of 50MV/m and a volume resistance of 10 13 ～10 15 Omega cm, a relative permittivity of 3, a dielectric loss tangent of about 10 －3 The good insulation performance can be maintained in a wide temperature and frequency range; in addition, the silicone resin also has excellent moisture resistance, water resistance, rust resistance, cold resistance, ozone resistance and weather resistance, and has good corrosion resistance to most of chemical reagents containing water (such as dilute mineral acid), so that the silicone resin is widely applied.
However, silicone resins have disadvantages in terms of curability, adhesion, solvent resistance, mechanical strength, and the like, and thus limit the range of applications. Different organic synthetic resins have different advantages and disadvantages, while the disadvantage of silicone resins is precisely the advantage of certain organic synthetic resins. If organic silicon is introduced into organic synthetic resin or the organic synthetic resin is used for modifying the silicon resin, a novel resin with excellent performances of the silicon resin and the organic resin can be formed, so that the application value of the resin is further improved, and the application field of the resin is expanded. There are two general modification modes: physical modification and chemical modification.
Physical modification, namely combining the organic resin and the organic silicon resin by a physical method, can be divided into a simple blending method and a third phase adding method. The simple blending is to directly mix the organic resin and the organic silicon, so that although some performances of the organic resin can be improved, the organic silicon resin and the organic resin have large difference in solubility elucidation and cross compatibility, and under the condition of direct mixing, the organic silicon has precipitation phenomenon, is enriched on the surface and is easy to generate microphase separation. The occurrence of dangerous separation has great influence on the hardness, stability and mechanical properties of the modified resin, and the overall performance of the heaviest coating film is poor. In order to solve the problem of poor compatibility of the silicone resin with the organic resin, a method of adding the third item has been proposed. The method is to add a third substance, such as an organosilicon coupling agent, to a mixed system of organosilicon and organic resin. This material is compatible with both the silicone resin and the organic resin so that it acts as a mesophase to bind the silicone resin and the organic resin together. In this way, the compatibility of the two can be greatly enhanced, so that the stability of the mixed system is enhanced. In addition, the method for improving the two-phase compatibility comprises the following steps: the polarity of the pendant organic resin groups is improved to improve compatibility. Polysiloxane particles are prepared, mixed into an organic resin and cross-linked to cure to improve compatibility, etc.
The chemical modification method is to combine the organic silicon resin and the organic resin mainly through a copolymerization method. Copolycondensation is a relatively common method. The copolymerization is to utilize active end groups on the organosilicon, such as hydroxyl, amino, carboxyl, vinyl, epoxy groups of alkoxy in the organic resin, hydroxyl and other functional groups to react, so as to produce a grafted or blocked high polymer, thereby solving the problem of compatibility, introducing stable and flexible Si-O chains into a cured structure, and improving the chain breakage toughness of the organic resin. The common organic resins of the modified silicone resin are alkyd resin, polyester resin, epoxy resin, phenolic resin, acrylic resin and polyurethane. However, the related research work of the silicon resin modified by the hydrocarbon petroleum resin is not reported.
Disclosure of Invention
The invention aims to provide a synthesis method of hydrocarbon petroleum resin modified silicone resin, which aims to solve the technical problems that the silicone resin in the prior art has defects in curing, adhesion, solvent resistance, mechanical strength and the like, so that the application range of the silicone resin is limited.
The invention is realized in such a way that the hydrocarbon petroleum resin is used as a basic raw material, hydrocarbon petroleum resin is used as a modifier, and free radical graft polymerization is initiated in the presence of an organic peroxide initiator to prepare the hydrocarbon petroleum resin.
The invention further adopts the technical scheme that: the silicon resin is one or more of methyl silicon resin, methyl phenyl silicon resin and methyl vinyl silicon resin.
The invention further adopts the technical scheme that: the silicon resin is used in an amount of 50wt% to 99wt%.
The invention further adopts the technical scheme that: the hydrocarbon petroleum resin is a plurality of types of hydrocarbon petroleum resins prepared from petroleum cracking products.
The invention further adopts the technical scheme that: the dosage of the hydrocarbon petroleum resin is 50-1 wt%.
The invention further adopts the technical scheme that: the organic peroxide initiator is a peroxy acyl initiator or a peroxy di-tertiary alkyl initiator.
The invention further adopts the technical scheme that: the organic peroxide initiator comprises dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide and di-tert-butyl peroxide; the dosage of the organic peroxide initiator is 0.1-5% of the total weight of the raw materials.
The invention further adopts the technical scheme that: the free radical graft polymerization is solution polymerization, and the organic solvent comprises aliphatic hydrocarbon, petroleum ether, halogenated hydrocarbon, toluene and xylene; the dosage range of the organic solvent is 2-100 parts.
The invention further adopts the technical scheme that: the organic solvent is petroleum ether or toluene.
The invention further adopts the technical scheme that: the solution polymerization comprises the following steps: step S1: and (3) material co-dissolution: after the material system is replaced by nitrogen to be airtight, adding an organic peroxide initiator, hydrocarbon petroleum resin, silicone resin and an organic solvent into a mixer through a metering pump according to a proportion, and uniformly stirring the mixture at a required temperature until the resin is completely dissolved to form a viscous and homogeneous co-solvent; step S2: and (3) synthesis reaction: controlling the temperature of the mixer to be 70-90 ℃, starting timing, and continuing the reaction for 1-3 hours; then, raising the temperature to enable the temperature of the materials in the mixer to be 100-140 ℃, and reacting for 1-2 hours at the temperature to obtain a silicon carbide petroleum resin mixed solution; step S3: product separation: and (3) conveying the silicon carbide petroleum resin mixed solution to a rotary distillation device at 50-150 ℃ through a cooling device, distilling and separating low-boiling-point substances under high vacuum degree to obtain silicon carbide petroleum resin, conveying the low-boiling-point substances to a solvent recovery tank for refining and recycling, and cooling the silicon carbide petroleum resin and granulating by a granulator.
The beneficial effects of the invention are as follows: the hydrocarbon silicon petroleum resin utilizes the advantages of low price, good compatibility, viscosity increment, thermal stability and the like of hydrocarbon petroleum resin, adopts a free radical grafting polymerization process to modify the organic silicon resin, reduces the cost of a target product, simultaneously ensures that the target product has the characteristics of self high and low temperature resistance, weather aging resistance, corrosion resistance and the like, has the characteristics endowed by the organic resin, can realize the production technical requirements by adopting a free radical grafting polymerization principle, and can expand the industrial application fields of the hydrocarbon silicon petroleum resin, such as anticorrosive paint, insulating paint, pressure sensitive adhesive and the like.
Detailed Description
The invention provides a synthesis method of hydrocarbon petroleum resin modified silicone resin, which takes silicone resin as a basic raw material, hydrocarbon petroleum resin as a modifier, and initiates free radical graft polymerization in the presence of an organic peroxide initiator to prepare hydrocarbon silicone petroleum resin.
The silicon resin is one or more of methyl silicon resin, methyl phenyl silicon resin and methyl vinyl silicon resin. The silicon resin is used in an amount of 50wt% to 99wt%.
The hydrocarbon petroleum resin is a plurality of types of hydrocarbon petroleum resins prepared from petroleum cracking products. The dosage of the hydrocarbon petroleum resin is 50-1 wt%.
The organic peroxide initiator is a peroxy acyl initiator or a peroxy di-tertiary alkyl initiator. The organic peroxide initiator comprises dibenzoyl peroxide (BPO), dilauryl peroxide (LPO), dicumyl peroxide (DCP), and di-tert-butyl peroxide (DTBP), preferably dibenzoyl peroxide (BPO) or dicumyl peroxide (DCP); the dosage of the organic peroxide initiator is 0.1-5% of the total weight of the raw materials.
The free radical graft polymerization is solution polymerization, and the organic solvent comprises aliphatic hydrocarbon, petroleum ether, halogenated hydrocarbon, toluene and xylene; the amount of the organic solvent is in the range of 2 to 100 parts (parts by weight are kg or g, and parts by volume are l or ml). The organic solvent is petroleum ether or toluene.
The solution polymerization comprises the following steps: step S1: and (3) material co-dissolution: after the material system is replaced by nitrogen to be airtight, adding an organic peroxide initiator, hydrocarbon petroleum resin, silicone resin and an organic solvent into a mixer through a metering pump according to a proportion, and uniformly stirring the mixture at a required temperature until the resin is completely dissolved to form a viscous and homogeneous co-solvent; step S2: and (3) synthesis reaction: controlling the temperature of the mixer to be 70-90 ℃, starting timing, and continuing the reaction for 1-3 hours; then, raising the temperature to enable the temperature of the materials in the mixer to be 100-140 ℃, and reacting for 1-2 hours at the temperature to obtain a silicon carbide petroleum resin mixed solution; step S3: product separation: and (3) conveying the silicon carbide petroleum resin mixed solution to a rotary distillation device at 50-150 ℃ through a cooling device, distilling and separating low-boiling-point substances under high vacuum degree to obtain silicon carbide petroleum resin, conveying the low-boiling-point substances to a solvent recovery tank for refining and recycling, and cooling the silicon carbide petroleum resin and granulating by a granulator.
The rotary distillation apparatus used therein may be an atmospheric distillation column bottoms apparatus, a vacuum distillation column bottoms apparatus, or the like; the cooling device can cool the air cooler, the water cooler or the low-temperature refrigerant.
The hydrocarbon silicon petroleum resin utilizes the advantages of low price, good compatibility, viscosity increment, thermal stability and the like of hydrocarbon petroleum resin, adopts a free radical grafting polymerization process to modify the organic silicon resin, reduces the cost of a target product, simultaneously ensures that the target product has the characteristics of self high and low temperature resistance, weather aging resistance, corrosion resistance and the like, has the characteristics endowed by the organic resin, can realize the production technical requirements by adopting a free radical grafting polymerization principle, and can expand the industrial application fields of the hydrocarbon silicon petroleum resin, such as anticorrosive paint, insulating paint, pressure sensitive adhesive and the like.
Properties for hydrocarbon silicone petroleum resins include: the light transmittance, the melting point, the water contact angle, the water absorption and other properties and performances adopt corresponding instruments: the ultraviolet-visible light spectrophotometer, capillary melting point tester, microcomputer controlled water contact angle tester, according to the relative test method, the water absorption rate according to the national standard GB-T1034-2008 plastic water absorption determination method, each group of test samples (batch) number is not less than 5, the test result is the average value of the multiple measurement data.
The description will be given by way of examples.
The hydrocarbon silicon petroleum resin prepared by adopting free radical graft polymerization comprises the following raw materials: silicone resin: 50-99 wt% of hydrocarbon petroleum resin: 50-1 wt% of petroleum ether: 2 to 100 volume parts (kilogram or gram, volume part is liter or milliliter), and the organic peroxide initiator is 0.1 to 5 weight percent of the total weight of the raw materials.
Embodiment one to embodiment five.
Examples one to five according to the formulation in table 1, the reaction materials were placed in a reaction vessel equipped with a stirring device, a reflux condensing device, a nitrogen protection device and a thermometer, and after nitrogen substitution for 10 minutes, the resin materials were gradually heated and dissolved under slow stirring, and then gradually heated to 70 to 90 ℃ under stirring to react for 2 to 3 hours, and further heated to 100 to 140 ℃ to react for 1 to 2 hours, and the reaction was completed.
And switching the reflux condensing device into a reduced pressure distillation device, or introducing the materials into a vacuum reduced pressure rotary distillation device, gradually heating to 150 ℃ under the vacuum degree of-0.095 MPa to remove the solvent and the low-boiling-point substances, and obtaining the silicon carbide petroleum resin with the product rate of not less than 99%.
TABLE 1 formulation composition of the examples
Description: in the first to third embodiments, methyl silicone resin is adopted, toluene is adopted as an organic solvent, and BPO is adopted as an organic peroxide initiator; in the fourth to fifth embodiments, the methyl phenyl silicone resin, the organic solvent is petroleum ether, the organic peroxide initiator is DCP, and the hydrocarbon petroleum resin is C9 petroleum resin.
The silicon carbide petroleum resins synthesized in examples one to five were subjected to melting point, water contact angle, 24h water absorption, 48h water absorption and light transmittance at 400nm to 800nm according to the above description, and the results of performance test of the products prepared in each example are shown in Table 2.
TABLE 2 Performance test results of the products prepared in the examples
As can be seen from the test results, compared with the silicon resin raw material of a certain company, the prepared silicon carbide petroleum resin has obviously changed in the aspects of hot melting temperature, water contact angle, water absorption, light transmittance and the like.
The hydrocarbon silicon petroleum resin is obtained through free radical grafting polymerization reaction, and the melting point of the modified resin is continuously reduced along with the gradual increase of the modification proportion of the hydrocarbon petroleum resin. The introduction of hydrocarbon petroleum resin has the tendency of slightly decreasing the water contact angle of silicon carbide resin as a whole, but is not remarkable, and has little influence on hydrophilicity and hydrophobicity. With the gradual increase of the proportion of the hydrocarbon petroleum resin, the 24-hour water absorption and the 48-hour water absorption of the modified silicone resin sample are both in a decreasing trend, and the introduction of the hydrocarbon petroleum resin into the silicone resin is beneficial to reducing the hygroscopicity of the silicone resin.
Therefore, the hydrocarbon silicon petroleum resin prepared by the synthesis method of the hydrocarbon petroleum resin modified silicon resin is obviously improved in the aspects of hot melting temperature, hydrophilic performance and the like, effectively expands the application scene in the industrial field, and has wide application prospect in the material fields of anticorrosive paint, insulating paint, pressure-sensitive adhesive and the like.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A synthesis method of hydrocarbon petroleum resin modified silicone resin is characterized in that the synthesis method takes silicone resin as a basic raw material, hydrocarbon petroleum resin as a modifier, and free radical graft polymerization is initiated in the presence of an organic peroxide initiator to prepare the hydrocarbon silicone petroleum resin.
2. The method of synthesis according to claim 1, wherein the silicone resin is one or more of methyl silicone resin, methyl phenyl silicone resin and methyl vinyl silicone resin.
3. The method of synthesis according to claim 2, wherein the amount of silicone resin is 50 to 99wt%.
4. The method of claim 1, wherein the hydrocarbon petroleum resin is a plurality of types of hydrocarbon petroleum resins derived from petroleum cracking products.
5. The method according to claim 4, wherein the hydrocarbon petroleum resin is used in an amount of 50wt% to 1wt%.
6. The method of synthesis according to claim 1, wherein the organic peroxide initiator is a peroxy acyl initiator or a di-tertiary alkyl peroxide initiator.
7. The method of synthesis according to claim 6, wherein the organic peroxide initiator comprises dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide; the dosage of the organic peroxide initiator is 0.1-5% of the total weight of the raw materials.
8. The synthetic method according to any one of claims 1 to 7, wherein the radical graft polymerization is a solution polymerization, and the organic solvent thereof includes aliphatic hydrocarbons, petroleum ether, halogenated hydrocarbons, toluene, xylene; the dosage range of the organic solvent is 2-100 parts.
9. The synthetic method of claim 8 wherein the organic solvent is petroleum ether or toluene.
10. The synthetic method of claim 9 wherein the solution polymerization comprises the steps of: step S1: and (3) material co-dissolution: after the material system is replaced by nitrogen to be airtight, adding an organic peroxide initiator, hydrocarbon petroleum resin, silicone resin and an organic solvent into a mixer through a metering pump according to a proportion, and uniformly stirring the mixture at a required temperature until the resin is completely dissolved to form a viscous and homogeneous co-solvent; step S2: and (3) synthesis reaction: controlling the temperature of the mixer to be 70-90 ℃, starting timing, and continuing the reaction for 1-3 hours; then, raising the temperature to enable the temperature of the materials in the mixer to be 100-140 ℃, and reacting for 1-2 hours at the temperature to obtain a silicon carbide petroleum resin mixed solution; step S3: product separation: and (3) conveying the silicon carbide petroleum resin mixed solution to a rotary distillation device at 50-150 ℃ through a cooling device, distilling and separating low-boiling-point substances under high vacuum degree to obtain silicon carbide petroleum resin, conveying the low-boiling-point substances to a solvent recovery tank for refining and recycling, and cooling the silicon carbide petroleum resin and granulating by a granulator.
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