CN112300518A - TDI-DBP-based PVC cross-linking agent - Google Patents
TDI-DBP-based PVC cross-linking agent Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a TDI-DBP (toluene diisocynate) -based PVC (polyvinyl chloride) crosslinking agent, which comprises the following components in percentage by weight: 10-30 parts; dibutyl phthalate DBP: 60-100 parts; catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion; 1-2 parts of a stabilizer; flame retardant: 1 to 2 portions. The invention also discloses a method for preparing the cross-linking agent and a PVC material based on the cross-linking agent. The PVC cross-linking agent is suitable for products such as industrial conveying belts, running belts, coated cloth, tarpaulin and the like. Compared with other products on the market, the product of the invention can meet the European Union national standard, when the specifications of the base fabric, the sizing gram number, the temperature, the vehicle speed, the same proportion and other process parameters are the same, the peel strength is good, the development time is long, the tearing degree is high, the softness is good, and the finally generated terminal product has high weather resistance, and the longest time can reach 12 years.
Description
Technical Field
The invention relates to the technical field of cross-linking agents, in particular to a TDI-DBP (toluene diisocynate-DBP) -based PVC cross-linking agent.
Background
The polyvinyl chloride paste resin has a fine particle size, is like talc in texture, and has no flowability. Polyvinyl chloride paste resins are mixed with plasticizers and stirred to form a stable suspension, i.e. to form a PVC paste, or PVC plastisol, PVC sol, and are used in this form for processing into finished products. During the paste making process, various fillers, diluents, heat stabilizers, foaming agents, light stabilizers and the like are added according to different product requirements.
The development of the PVC paste resin industry provides a new liquid material which becomes a polyvinyl chloride product upon heating only. The liquid material has the advantages of convenient preparation, stable performance, easy control, convenient use, excellent product performance, good chemical stability, certain mechanical strength, easy coloring and the like, thereby being widely applied to the production of artificial leather, vinyl toys, soft trademarks, wallpaper, paint coatings, foamed plastics and the like.
PVC paste resins are known for paste processing as highly dispersible powders. The paste forming performance is excellent, and the dispersion performance is good, so that the paste is mainly applied to the field of soft materials of PVC resin. The coating can be applied to the processing technologies of coating, dipping, spraying, foaming and the like, and can be widely applied to the fields of various materials and products such as artificial leather, decorative materials, floor leather, wall paper, industrial conveying belts, sports grounds, coatings, cross-linking agents, toys, medical disposable gloves, daily decorative materials, electrical instruments, electrical tools and the like.
The PVC paste resin molding processing has the advantages of low equipment price, simple and cheap processing mold, capability of being made into special shapes, easiness in foaming, few heating times of products, capability of producing a small amount of products in various varieties and the like, so that the PVC paste resin molding processing is widely applied to hard products such as artificial leather, floor leather, toys, wallpaper, automotive interior materials and the like, and has wide market application prospect.
From the above, it can be seen that the PVC paste resin has various uses. In the prior art, PVC paste resin has good bonding effect with coarse fibers such as cotton, but the surface of synthetic fibers is smooth and has no bonding effect on paste. Therefore, it is necessary to add a binder to the paste to improve the adhesion of the smooth surface synthetic fibers to the PVC paste resin.
The prior art discloses a method for preparing a composite material of PVC paste resin and fiber.
Document 1: CN201911216899.X discloses a flame-retardant waterproof and tarpaulin of nanometer PVC and a preparation method thereof, wherein the flame-retardant waterproof and tarpaulin of nanometer PVC is prepared by dipping and coating synthetic fiber base cloth with PVC nanometer flame-retardant plastisol, completely permeating tiny particles of nanometer penetrant into fiber gaps of the base cloth, flattening by a flattening machine, heating and plasticizing by an oven to prepare a cover film with flat and smooth two surfaces, and has good water permeability resistance. Solves the problems of water resistance, easy falling off of the tarpaulin covering film and skin breaking in the prior art. Synthetic vegetable fatty acid ester with flame retardant property and polishing slag with flame retardant and smoke suppression properties are added in the formula, so that the problem of flame retardant property reduction caused by the addition of a large amount of small-molecule plasticizer in the prior art is solved. The polishing slag is added as an inorganic filler in a large amount, so that the production cost is reduced, the flame retardant and smoke suppression performances of the PVC flame-retardant waterproof tarpaulin are improved, and the problems of environmental pollution caused by the fact that the polishing slag of stone materials, ceramic tiles and artificial stones is difficult to recycle and the waste landfill is solved.
Document 2: CN 201911216897.0; a flame-retarding and antistatic nano fabric for the wind tube is prepared through immersing synthetic fibre fabric in flame-retarding and antistatic PVC plastisols containing nano penetrant, pressing by flatting machine, heating in baking oven, plasticizing to obtain smooth covering film, and cooling. The plastisol completely permeates into the synthetic fiber, and the problem that the cover film is easy to fall off and the skin is broken to cause air leakage of the air duct in the prior art is solved. Synthetic vegetable fatty acid ester with flame retardant and antistatic properties and stone, ceramic tile and artificial stone polishing slag with flame retardant and smoke suppression properties are added in the formula, so that the problem of flame retardant property reduction caused by the addition of a large amount of small molecular plasticizers in the prior art is solved. The polishing slag is added in a large amount as an inorganic filler, so that the production cost is reduced, the flame retardant and smoke suppression performance of the product is improved, the problems that the polishing slag is difficult to recycle and the environment is polluted due to waste landfill are solved, and waste is changed into valuable.
Document 3: CN 201310506209.0; the artificial leather comprises a base material layer, an adhesive layer, a soft foaming layer and a mirror layer, wherein the adhesive layer is positioned between the base material layer and the soft foaming layer, and the mirror layer is positioned on the upper surface of the soft foaming layer. The manufacturing process method comprises the following steps: firstly, coating a bonding layer on a substrate layer, then coating and scraping PVC (polyvinyl chloride) plastisol on plain release paper to foam at high temperature and attach the PVC plastisol on the bonding layer, or directly coating the PVC plastisol on the substrate to foam at high temperature to prepare a soft foaming layer; then the mirror material is rolled and compounded on the surface of the soft foaming layer, and the high-performance soft composite mirror artificial leather is prepared. The invention solves the technical problem of modifying and processing the high-performance mirror-surface artificial leather by adopting the coating substrate for foaming and calendering the mirror surface, not only improves the softness of the mirror-surface artificial leather, but also improves the surface folding resistance, and has simple process.
It can be seen from the above documents that, in the prior art, no crosslinking agent is added in the process of compounding the PVC paste resin and the synthetic fiber, or the bonding effect of the crosslinking agent is poor. Based on this, the technical problem to be solved by the present invention is to provide a crosslinking agent which can achieve better bonding effect between the PVC paste and the synthetic fiber for a longer period of time.
Disclosure of Invention
The invention aims to provide a TDI-DBP-based PVC cross-linking agent.
The technical problems solved by the invention are as follows: in the prior art, the PVC paste resin and coarse fibers have good bonding effect and can be made into products, but the bonding capability between the existing PVC paste resin and synthetic fibers is very poor, so that the PVC paste resin cannot well form composite required bonding force with smooth synthetic fibers.
In order to achieve the above object, an embodiment of the present invention provides a TDI-DBP based PVC crosslinking agent, comprising the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4-30%.
Preferably, the PVC crosslinking agent of the present invention comprises the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts; 10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4-30%.
Preferably, the stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
Preferably, the PVC crosslinking agent of the present invention comprises the following components:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part; 10 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 3000-5000 mPa & s; the NCO content is 4-20%.
Based on the PVC cross-linking agent, the invention discloses a method for preparing the PVC cross-linking agent, which comprises the following steps:
(1) preparing all raw materials according to a ratio;
(2) adding a plasticizer dibutyl phthalate and a catalyst phenol into a reaction kettle, heating to 80-120 ℃, dropwise adding toluene diisocyanate TDI for reacting for 5-8 h, adding the rest raw materials after dropwise adding, and then carrying out heat preservation reaction at 100-120 ℃ to remove residual monomers;
(2) and (5) after the heat preservation reaction is finished, cooling to normal temperature, filtering, and sealing and packaging.
Based on the PVC cross-linking agent, the invention also discloses a PVC material for bonding with the synthetic fiber, which comprises the PVC cross-linking agent and PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts; 10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
In summary, the invention has the following advantages:
1. according to the invention, by optimizing the components of the PVC cross-linking agent, better bonding capacity can be generated between the PVC paste and the smooth synthetic fiber, and the product prepared by applying the PVC cross-linking agent has higher peel strength and tear resistance, good weather resistance and long service life.
2. By applying the PVC cross-linking agent disclosed by the invention, products prepared under the conditions that the specifications of base fabrics are the same, the grams of sizing are the same, the temperature is the same, the vehicle speed is the same, and the proportion is the same have the advantages of long development time, high tearing strength, good softness and high weather resistance of terminal products, and the maximum time can reach 12 years.
3. The invention belongs to a PVC cross-linking agent, which is suitable for products such as industrial conveying belts, running belts, coated cloth, tarpaulin and the like.
Detailed Description
The invention discloses a TDI-DBP (toluene diisocynate-DBP) -based PVC (polyvinyl chloride) crosslinking agent, which comprises the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts;
the viscosity of the cross-linking agent is 2000-7000 mPas;
the NCO content is 4-30%.
In a preferred embodiment of the invention, the PVC cross-linking agent comprises the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts;
10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas;
the NCO content is 4-30%.
In a preferred embodiment of the present invention, the stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
In a preferred embodiment of the invention, the PVC cross-linking agent comprises the following components:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part; 10 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 3000-5000 mPa & s;
the NCO content is 4-20%.
The method for preparing the PVC cross-linking agent comprises the following steps:
(1) preparing all raw materials according to a ratio;
(2) adding a plasticizer dibutyl phthalate and a catalyst phenol into a reaction kettle, heating to 80-120 ℃, dropwise adding toluene diisocyanate TDI for reacting for 5-8 h, adding the rest raw materials after dropwise adding, and then carrying out heat preservation reaction at 100-120 ℃ to remove residual monomers;
(2) and (5) after the heat preservation reaction is finished, cooling to normal temperature, filtering, and sealing and packaging.
The invention discloses a PVC material for bonding with synthetic fibers, which comprises a PVC cross-linking agent and a PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts; 10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas;
the NCO content is 4% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
Example 1:
a TDI-DBP based PVC crosslinker comprising the following components:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part;
the viscosity of the cross-linking agent is 3000-5000 mPa & s;
the NCO content is 4-20%.
The stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
Example 2:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part; 10 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 3000-5000 mPa & s; the NCO content is 4-20%.
The stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
Example 3:
a PVC material for bonding with synthetic fibers comprises a PVC crosslinking agent and a PVC plasticizing paste, wherein 4.5 percent of the PVC crosslinking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part; 10 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 3000-5000 mPa & s; the NCO content is 4-20%.
The stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
Wherein the PVC plasticizing paste comprises:
100 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 60 parts;
2.5 parts of stabilizer barium and zinc;
40 parts of calcium carbonate.
Experimental example 1: adhesion test
The experimental method comprises the following steps: the cross-linking agent of the invention, example 1, was added to the PVC plasticising paste in an amount of 4.5%, and the viscosity of the mixture was measured in mPa · s using a model NDJ-1 viscometer every 10min after the addition of the cross-linking agent; the change in viscosity over 1h of crosslinker addition is shown in Table 1:
table 1: adhesion test results
| Time min | Viscosity mPas | Time of day | Viscosity of the oil |
| 0 | 3800 | 40 | 4550 |
| 10 | 4000 | 50 | 4700 |
| 20 | 4120 | 60 | 4950 |
| 30 | 4360 |
And (4) experimental conclusion:
the viscosity has a large influence on the production, and when the viscosity is extremely large or the rate of change of the viscosity is high, the production is liable to be adversely affected, and for example, when the change value of the viscosity within 1 hour is more than 10000 mPas, the industrial production is not suitable. The viscosity of the product prepared by the formula and the method is increased from 3800 to 4950 within 1h, and the product can meet the production requirement.
Experimental example 2: relationship between product molding time and peel strength
The experimental method comprises the following steps: the PVC plasticising paste obtained in example 3 was mixed with the cross-linking agent of the invention of example 1, the addition of which was 4.5%. After the cross-linking agent is added, the mixed material is uniformly coated on high-strength industrial polyester yarns made of synthetic fiber materials with 1100dtex and 1100dtex in both warp direction and weft direction by a scraper, the weaving density is 23 pieces/inch, the gram weight of the coating per square meter is controlled at 250g, and the polyester yarns are placed in a 200 ℃ oven for plasticizing for 1 min.
Cooling after plasticizing, cutting into five large sample blocks of 50cm by 200cm, carrying out heat sealing on the large sample blocks by using a high-frequency heat sealing machine, and then cutting into 4 small sample blocks;
then, the peel strength of each small sample block was measured using a universal tensile machine, and 4 small sample blocks were re-measured at intervals of 1 month during and after molding, respectively, with the measurement results shown in table 2:
table 2: detection results of peel strength of small sample blocks in different forming times
And (4) experimental conclusion:
after the cross-linking agent in the embodiment 1 of the invention reacts with the PVC plasticizing paste, the peel strength is improved for a long time after the PVC plasticizing paste is formed with a synthetic fiber product, and the maximum peel strength can reach more than 120 months. The PVC cross-linking agent disclosed by the invention is low in cost and high in performance-price ratio.
Experimental example 3: environmental restriction detection
The PVC cross-linker of the invention complies with the correction directive of European Pump ROHS directive 2011/65EU appendix two and with the EU2015/863 heavy metal restriction requirements, using SGS tests.
Experimental example 4: peel Strength comparison of different PVC crosslinkers
The experimental method comprises the following steps: experiments are carried out by using different PVC cross-linking agents, after different components are verified to be mixed with the PVC plasticizing paste, a plurality of small sample blocks are prepared by the method in the experimental example 2, then the peeling strength of each small sample block is detected by using a universal tensile machine, and the detection is carried out on 4 small sample blocks respectively at intervals of 1 month during and after the forming. Wherein the composition of the different groups of PVC crosslinkers is shown in table 3.
Table 3: composition of PVC crosslinking agent in Experimental example 4
Cetearyl alcohol is a common chemical raw material, which is mainly used for lubricants, emulsifiers and antifoaming agents, and occasionally for tackifiers.
Thus, controls 1 to 4 of the present invention were examined whether the role played by cetearyl alcohol in the PVC cross-linking agent was due to its lubricating, emulsifying, antifoaming or viscosifying effect. The peel strength was measured by the method of example 2 in seven experimental groups of experimental example 4 of the present invention, and the average value of the measurement results is shown in table 4 below.
Table 4: test results of Experimental example 4
The blank control contained no substance, i.e., the PVC plasticizing paste was directly coated on the synthetic fiber cloth, and then the same procedure as in experimental example 2 was carried out to prepare a sample block, and the relevant peel strength was measured. The blank control was used to verify the adhesion between the PVC paste resin and the synthetic fiber cloth without the use of PVC crosslinker.
From the above experiments, it can be seen that the blank group had the lowest peel strength and did not develop a tendency to strengthen over time, indicating that the PVC plasticized paste is difficult to crosslink with smooth synthetic fiber cloth and does not develop good adhesion when the PVC binder is no longer suitable.
In the embodiment 2 of the present invention, a single component of cetearyl alcohol is added on the basis of the original embodiment 1, and the peel strength of the product is significantly increased after the cetearyl alcohol is added, which shows that the bonding capability between the PVC plasticizing paste and the synthetic fiber can be significantly improved after the cetearyl alcohol is added.
Compared with example 1, the control group 1 to the control group 4 respectively increase different single components, but the peel strength of the control group 1 to the control group 4 is not significantly different from that of the example 1, which indicates that the increase of the single component does not improve the peel strength and has no obvious effect. Therefore, it can be seen that the present invention does not show the substantial increase in peel strength in example 2 in the control group in which the lubricant, emulsifier, defoamer and tackifier are added, and thus it can be demonstrated that cetearyl alcohol, a single component, added in example 2, can increase the adhesive strength between the PVC plasticized paste and the synthetic fiber. However, when cetearyl alcohol alone was used, it was not possible to improve the bonding strength of the PVC plasticising paste to the synthetic fibres, and it was thus seen that the addition of cetearyl alcohol to the composition of example 1 promotes the cross-linking ability of the original PVC cross-linking agent.
Claims (6)
1. A TDI-DBP-based PVC crosslinking agent is characterized by comprising the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4-30%.
2. The PVC crosslinking agent of claim 1, comprising the following components:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts; 10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4-30%.
3. The PVC crosslinking agent according to claim 1 or 2, wherein: the stabilizer is a methyl tin heat stabilizer; the flame retardant is aluminum hydroxide.
4. The PVC crosslinking agent according to claim 1 or 2, wherein: comprises the following components:
toluene diisocyanate TDI: 20 parts of (1);
dibutyl phthalate DBP: 80 parts of a mixture;
catalyst phenol: 2 parts of (1); peony essence: 0.5 part;
2 parts of a stabilizer; flame retardant: 1 part; 10 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 3000-5000 mPa & s; the NCO content is 4-20%.
5. A process for preparing the PVC crosslinking agent of any one of claims 1 to 4, comprising the steps of:
(1) preparing all raw materials according to a ratio;
(2) adding a plasticizer dibutyl phthalate and a catalyst phenol into a reaction kettle, heating to 80-120 ℃, dropwise adding toluene diisocyanate TDI for reacting for 5-8 h, adding the rest raw materials after dropwise adding, and then carrying out heat preservation reaction at 100-120 ℃ to remove residual monomers;
(2) and (5) after the heat preservation reaction is finished, cooling to normal temperature, filtering, and sealing and packaging.
6. A PVC material for bonding with synthetic fiber is characterized by comprising a PVC cross-linking agent and a PVC plasticizing paste, wherein 3-6% of the PVC cross-linking agent is added into each 100 parts of the PVC plasticizing paste;
wherein the PVC cross-linking agent comprises:
toluene diisocyanate TDI: 10-30 parts;
dibutyl phthalate DBP: 60-100 parts;
catalyst phenol: 1-3 parts; peony essence: 0.1 to 1 portion;
1-2 parts of a stabilizer; flame retardant: 1-2 parts; 10-20 parts of cetearyl alcohol;
the viscosity of the cross-linking agent is 2000-7000 mPas; the NCO content is 4% -30%;
wherein the PVC plasticizing paste comprises:
80-150 parts of PVC resin;
plasticizer diisononyl phthalate DINP: 50-100 parts;
2-5 parts of stabilizer barium and zinc;
30-60 parts of calcium carbonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115340710A (en) * | 2022-06-30 | 2022-11-15 | 广元瑞峰新材料有限公司 | Environment-friendly plasticizing cross-linking agent and preparation method thereof |
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