CN112852381B - High-performance flame-retardant silane modified polyether sealant and preparation method thereof - Google Patents
High-performance flame-retardant silane modified polyether sealant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
- C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/08—Macromolecular additives
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a high-performance flame-retardant silane modified polyether sealant and a preparation method thereof, and relates to the technical field of sealants. The preparation method of the sealant specifically comprises the following steps: s1: mixing modified polysiloxane end-capped polyether, a plasticizer, a water removing agent, calcium carbonate, white carbon black and a flame-retardant filler to obtain a product A; s2: mixing the product A obtained in the step S1 with a tackifier, and adding an organic chelated tin catalyst for reaction; and (4) carrying out vacuum defoaming treatment, stirring, discharging and sealing to obtain the sealant. The prepared sealant has excellent flame retardance, good mechanical property, good elasticity, high bonding property, good corrosion resistance, high curing speed, outstanding high-temperature resistance and excellent product quality, and can be widely used.
Description
Technical Field
The invention belongs to the technical field of sealants, and particularly relates to a high-performance flame-retardant silane modified polyether sealant and a preparation method thereof.
Background
The sealant is a multifunctional bonding sealing material which has the functions of bonding, caulking and bearing deformation shrinkage stress of gaps at gaps or joints of different structures or base materials. Compared with the traditional bolt, riveting and the like, the sealant has polymer elastomers with excellent bonding, good elasticity, light weight, high strength and strong corrosion resistance, and is widely applied to the technical fields of heavy engineering such as buildings, automobiles, mechanical manufacturing, energy and electrical engineering and the like. However, with the increasing enhancement of environmental protection and safety awareness, the existing sealant has two problems: (1) the base material has high viscosity, and a large amount of organic solvent with strong volatility must be used as a diluent to reduce the viscosity in order to realize convenient construction, so that the base material is not only harmful to human health, but also can destroy the atmospheric ozone layer; (2) the base material has low curing speed at room temperature, and in order to improve the curing reaction speed, organic tin compounds are usually used as catalysts to shorten the curing time of the adhesive, but the catalysts have high toxicity and cause harm to the environment.
The silane modified polyether sealant is a functional polymer material which takes polyether as a molecular main chain and is terminated by alkoxy silane, and has the advantages of excellent weather resistance, durability, adhesiveness, finishing property, heat resistance, cold resistance, low contamination, environmental protection and the like due to the combination of the organic silicon and the polyurethane sealant. At present, the market share of silane modified polyether adhesive is rapidly increased, and the silane modified polyether adhesive becomes a new generation of high-performance high polymer sealing material.
The existing flame-retardant silane modified polyether sealant mainly achieves the purpose of flame retardance by adding additive flame retardants such as hydroxides, hypophosphite and the like. However, the additive flame retardant is easy to absorb moisture and poor in compatibility with the sealant matrix resin, and the mechanical property of the material is reduced due to the large amount of the additive flame retardant. Therefore, the preparation of a high-performance flame-retardant silane modified polyether sealant is a demand of the current market.
Disclosure of Invention
The invention aims to provide a high-performance flame-retardant silane modified polyether sealant and a preparation method thereof, wherein the sealant has excellent flame retardance, good mechanical property, good elasticity, high bonding property, good corrosion resistance, high curing speed and outstanding high-temperature resistance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the application of modified polysiloxane in sealant is characterized by that said modified polysiloxane is made up by using maleopimaric acid anhydride through a certain modification process. The maleopimaric anhydride has good thermal stability, polysiloxane is modified by the maleopimaric anhydride, and then the polyether is blocked, so that the prepared sealant has excellent flame retardant property, can maintain higher mechanical property, and effectively improves the tensile strength and elasticity of the sealant; the heat stability of the sealant is enhanced, and the sealant has excellent high-temperature resistance; in addition, the existence of the maleic pine umbellate neo-anhydride can also obviously improve the curing speed of the sealant, enhance the bonding property, improve the quality of the sealant and prolong the storage life which is more than 6 months. The preparation method is simple, the raw material proportion is reasonable, the sealant is prepared from nontoxic and harmless chemical products, and the prepared sealant has high flame retardant property and good mechanical property, and is convenient to popularize and use.
Preferably, the modified polysiloxane raw material components comprise, by weight, 10-14 parts of maleopimaric acid anhydride and 40-50 parts of polysiloxane.
Preferably, the specific preparation method of the maleopimaric acid anhydride comprises the following steps: taking pinocembrin acid, heating and preserving heat for a period of time under the protection of nitrogen; slowly adding maleic anhydride for reaction; and cooling in ice water, crushing, washing, drying, dissolving in glacial acetic acid, heating for refluxing, recrystallizing, washing and drying to obtain the product.
Preferably, the molar ratio of the maleic anhydride to the pinocembrin acid is 2-2.5: 1; the reaction temperature is 260-270 ℃.
Preferably, the raw material components of the polysiloxane comprise, by weight, 10-12 parts of aminosilane, 90-95 parts of octamethylcyclotetrasiloxane, 0.4-0.6 part of hexamethyldisiloxane and 0.1-0.2 part of potassium hydroxide.
The preparation method of the modified polysiloxane comprises the following steps: and (3) reacting the maleic pine umbellate neo-anhydride and polysiloxane for 4-5 hours at the temperature of 90-98 ℃ to obtain the modified polysiloxane.
A high-performance flame-retardant silane modified polyether sealant comprises the modified polysiloxane end-capped polyether, wherein the apparent viscosity of the polyether is 9000-15000 mPa & s.
The preparation method of the high-performance flame-retardant silane modified polyether sealant specifically comprises the following steps:
s1: mixing modified polysiloxane end-capped polyether, a plasticizer, a water removing agent, calcium carbonate, white carbon black and a flame-retardant filler to obtain a product A;
s2: mixing the product A obtained in the step S1 with a tackifier and a water removing agent, and adding an organic chelated tin catalyst and the water removing agent for reaction; and (4) carrying out vacuum defoaming treatment, stirring, discharging and sealing to obtain the sealant.
Preferably, the raw materials of the sealant comprise: the catalyst comprises, by weight, 90-120 parts of modified polysiloxane-terminated polyether, 90-110 parts of active nano calcium carbonate, 12-36 parts of polypropylene glycol, 2-4 parts of vinyl trimethoxy silane, 10-14 parts of white carbon black, 1-3 parts of bisaminosilane and 0.1-0.8 part of organic chelated tin catalyst.
Preferably, the mixing temperature in step S1 is 80-90 ℃ and the mixing time is 65-80 min.
Preferably, the mixing temperature in the step S2 is 20-40 ℃, and the time is 30-50 min; the reaction conditions are specifically as follows: the temperature is 20-40 ℃, and the time is 30-50 min.
Preferably, the water removing agent is added in two steps, and the total amount of the water removing agent is 1/3 in the step (1); and step S2, adding water removing agent with the total amount of 1/3 in the mixing process, and adding the rest water removing agent in the reaction process.
Preferably, the conditions of the vacuum degassing treatment may include, for example: the vacuum degree is-0.1 to-0.04 MPa, the temperature is 20 to 40 ℃, and the defoaming is carried out for 20 to 30min under the condition of 700 to 1200 rpm.
Preferably, the flame retardant filler is an intumescent flame retardant; the intumescent flame retardant comprises an acid source, a carbon source and a gas source, wherein the mass ratio of the acid source to the carbon source to the gas source is 2: 0.5-2: 0.5 to 2; wherein the acid source is one or more of ammonium polyphosphate (APP), melamine coated ammonium polyphosphate (MAPP) and melamine polyphosphate (MPP), the carbon source is one or more of Pentaerythritol (PER), Dipentaerythritol (DPER), Tripentaerythritol (TPER), phenolic resin (PF), starch (AM) and cyclodextrin (DT), and the gas source is one or more of melamine (M EL) and dicyandiamide (DCD/DICY).
More preferably, the flame-retardant filler is formed by uniformly dispersing magnesium orotate and an intumescent flame retardant, wherein the mass ratio of the magnesium orotate to the intumescent flame retardant is 1: 1.5 to 8. The sealant is added with the magnesium orotate, and has the functions of a sealant reinforcing agent and a flame retardant synergist. The flame retardant can effectively improve the flame retardant property of the sealant under the synergistic action of the flame retardant and the intumescent flame retardant; and the sealant can be compounded with other components, has an enhancement effect on the improvement of the performance of the sealant, further reduces the surface drying time, increases the curing speed and the tensile strength, and obviously improves the storage life. Besides, the corrosion resistance of the sealant can be effectively improved.
The invention also discloses the high-performance flame-retardant silane modified polyether sealant prepared by the method.
Of course, the high-performance flame-retardant silane modified polyether sealant does not exclude other additive components as long as the additive components do not affect the performance of the high-performance flame-retardant silane modified polyether sealant obtained by the invention. Examples of such additives include organic montmorillonite and diatomaceous earth. These additives may be added and mixed in any of the above steps as long as such addition does not affect the performance of the high performance flame retardant silane modified polyether sealant obtained in the present invention.
Compared with the prior art, the invention has the following beneficial effects:
the sealant prepared by modifying polysiloxane with maleopimaric anhydride and then capping polyether has excellent flame retardant property, effectively improves the tensile strength and elasticity of the sealant and enhances the thermal stability of the sealant; meanwhile, the existence of the maleic pine umbellate neo-anhydride can also obviously improve the curing speed of the sealant, reduce the surface drying time and enhance the cohesiveness, thereby obviously improving the quality of the sealant and prolonging the storage life. In addition, the magnesium orotate is added into the sealant and has synergistic effect with the intumescent flame retardant, so that the flame retardant property of the sealant can be effectively improved; and the sealant is compounded with other components for use, has a reinforcing effect on the improvement of partial performance of the sealant, and can also obviously improve the corrosion resistance of the sealant. The preparation method is simple, the raw material proportion is reasonable, the sealant is prepared from nontoxic and harmless chemical products, and the prepared sealant has high flame retardant property and good mechanical property, and is convenient to popularize and use.
Therefore, the high-performance flame-retardant silane modified polyether sealant and the preparation method thereof provided by the invention have the advantages of excellent flame retardance, good mechanical property maintenance, good elasticity, high bonding property, good corrosion resistance, high curing speed and outstanding high-temperature resistance.
Drawings
FIG. 1 shows the results of the infrared test in test example 1 of the present invention;
FIG. 2 is a schematic diagram showing results of the thermogravimetric analysis in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the organic chelated tin used in the examples of the present invention is chelated tin KRA-1, available from Kary chemical technology, Inc., Changzhou.
A process for the preparation of polysiloxanes comprising the steps of:
(1) reacting gamma-aminopropyl methyl diethoxy silane with deionized water (volume ratio is 1: 1) at 85 ℃ for 4 hours to obtain an aminosilane hydrolysate, wherein the volume ratio of the gamma-aminopropyl methyl diethoxy silane to the deionized water is 1: 1;
(2) dehydrating 12 parts by weight of aminosilane hydrolysate obtained in step (1), and reacting with 94 parts by weight of octamethylcyclotetrasiloxane, 0.6 part by weight of hexamethyldisiloxane, and 0.1 part by weight of potassium hydroxide at 140 ℃ for 5 hours to obtain polysiloxane.
Example 1:
preparing maleic pine tuckahoe new anhydride:
putting the pinocembrin neo-acid into a four-neck flask with stirring, a thermometer and nitrogen protection, and opening an oil bath kettle. Starting to introduce nitrogen for protection, heating to 260 ℃, and keeping the temperature for 30 min; slowly adding maleic anhydride (with molar ratio of 2: 1 to the pinocembrin acid) for multiple times, and reacting at 260 ℃ for 6 hours after the feeding is finished; discharging the crude product into ice water for cooling, crushing and washing with deionized water for multiple times to obtain the crude product, then drying, dissolving in glacial acetic acid, heating and refluxing for 2h, recrystallizing for two times, finally washing with deionized water for multiple times, and drying. The conversion (yield) was 86.9% by measurement of the acid value.
The maleic pine umbellate neo-anhydride modified polysiloxane is prepared by reacting 12 parts by weight of maleic pine umbellate neo-anhydride with 46 parts by weight of polysiloxane at 95 ℃ for 4.5 hours.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: 98 parts of modified polysiloxane-terminated polyether, 100 parts of active nano calcium carbonate, 28 parts of polypropylene glycol, 19 parts of flame-retardant filler, 3 parts of vinyl trimethoxy silane, 13 parts of white carbon black, 2 parts of bisaminosilane and 0.6 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 12500 mPas; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 1.2: 2; wherein the acid source is ammonium polyphosphate (APP), the carbon source is Tripentaerythritol (TPER), and the gas source is dicyandiamide (DCD/DICY).
The preparation method of the high-performance flame-retardant silane modified polyether sealant comprises the following steps:
s1: mixing modified polysiloxane-terminated polyether, polypropylene glycol, vinyl trimethoxy silane, active nano calcium carbonate and white carbon black at 85 ℃ for 70min to obtain a product A;
s2: mixing the product A obtained in the step S1 with bisaminosilane and vinyltrimethoxysilane at 40 ℃ for 40 min; then adding an organic chelated tin catalyst and vinyl trimethoxy silane for reaction at the temperature of 40 ℃ for 50 min; and (4) carrying out vacuum defoaming treatment, stirring, discharging and sealing to obtain the sealant. The conditions of the vacuum defoaming treatment include: the vacuum degree is-0.08 MPa, the temperature is 35 ℃, and the deaeration is carried out for 30min under the condition of 1000 rpm.
Wherein vinyltrimethoxysilane is added in two steps, vinyltrimethoxysilane in a total amount of 1/3 is added in step S1; step S2 Total amount of vinyltrimethoxysilane 1/3 of vinyltrimethoxysilane added during mixing and the remainder of the vinyltrimethoxysilane added during the reaction.
Example 2:
the preparation of maleopimaric anhydride and modified polysiloxane was the same as in example 1.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: 112 parts of modified polysiloxane-terminated polyether, 108 parts of active nano calcium carbonate, 30 parts of polypropylene glycol, 22 parts of flame-retardant filler, 4 parts of vinyl trimethoxy silane, 13 parts of white carbon black, 3 parts of bisaminosilane and 0.8 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 13600 mPas; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 0.9: 1.2; wherein the acid source is polyphosphoric acid melamine, the carbon source is phenolic resin (PF), and the gas source is melamine (M EL).
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Example 3:
the preparation of maleopimaric anhydride and modified polysiloxane was the same as in example 1.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: according to parts by weight, 95 parts of modified polysiloxane-terminated polyether, 101 parts of active nano calcium carbonate, 23 parts of polypropylene glycol, 16 parts of flame-retardant filler, 2 parts of vinyl trimethoxy silane, 11 parts of white carbon black, 1 part of bisaminosilane and 0.4 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 10500mPa · s; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 1.6: 1.3; wherein the acid source is melamine coated ammonium polyphosphate (MAPP), the carbon source is Pentaerythritol (PER), and the gas source is melamine (M EL).
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Example 4:
the preparation of maleopimaric anhydride and modified polysiloxane was the same as in example 1.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: 109 parts of modified polysiloxane-terminated polyether, 100 parts of active nano calcium carbonate, 17 parts of polypropylene glycol, 24 parts of flame-retardant filler, 3 parts of vinyl trimethoxy silane, 12 parts of white carbon black, 2 parts of bisaminosilane and 0.5 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 9600mPa · s; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 0.8: 0.9; wherein the acid source is ammonium polyphosphate (APP) and melamine coated ammonium polyphosphate (MAPP), the carbon source is Pentaerythritol (PER) and cyclodextrin (DT), and the gas source is melamine (M EL) and dicyandiamide (DCD/DICY).
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Example 5:
the preparation of maleopimaric anhydride and modified polysiloxane was the same as in example 1.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: 118 parts of modified polysiloxane-terminated polyether, 110 parts of active nano calcium carbonate, 34 parts of polypropylene glycol, 23 parts of flame-retardant filler, 4 parts of vinyl trimethoxy silane, 14 parts of white carbon black, 3 parts of bisaminosilane and 0.8 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 14000 mPas; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 0.5-2: 0.5 to 2; wherein the acid source is ammonium polyphosphate (APP), melamine coated ammonium polyphosphate (MAPP) and melamine polyphosphate (MPP), the carbon source is Pentaerythritol (PER), Dipentaerythritol (DPER), Tripentaerythritol (TPER) and starch (AM), and the gas source is dicyandiamide (DCD/DICY).
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Example 6:
the preparation of maleopimaric anhydride and modified polysiloxane was the same as in example 1.
A high-performance flame-retardant silane modified polyether sealant comprises the following raw material components: the modified polysiloxane-terminated polyether comprises, by weight, 94 parts of modified polysiloxane-terminated polyether, 103 parts of active nano calcium carbonate, 26 parts of polypropylene glycol, 14 parts of flame-retardant filler, 2 parts of vinyl trimethoxy silane, 10 parts of white carbon black, 1 part of bisamino silane and 0.3 part of organic chelated tin catalyst. Wherein the polyether has an apparent viscosity of 11500mPa · s; the flame-retardant filler is an intumescent flame retardant, and the mass ratio of the acid source to the carbon source to the gas source is 2: 0.9: 1.7; wherein the acid source is ammonium polyphosphate (APP), the carbon source is cyclodextrin (DT), and the gas source is melamine (M EL).
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Example 7:
the high-performance flame-retardant silane modified polyether sealant is different from the sealant in the embodiment 1 in that: in the preparation process step S1, the flame-retardant filler is formed by uniformly dispersing magnesium orotate and an intumescent flame retardant, wherein the mass ratio of the magnesium orotate to the intumescent flame retardant is 1: 1.8.
the preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Comparative example 1:
the high-performance flame-retardant silane modified polyether sealant is different from the sealant in the embodiment 1 in that: the modified polysiloxane-terminated polyether is replaced with a polysiloxane-terminated polyether.
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Comparative example 2:
the high-performance flame-retardant silane modified polyether sealant is different from the sealant in the embodiment 1 in that: dimethoxy terminated polyether is used in place of the modified polysiloxane terminated polyether.
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Comparative example 3:
the high-performance flame-retardant silane modified polyether sealant is different from the sealant in the embodiment 1 in that: the modified polysiloxane-terminated polyether is replaced by a triethoxy-terminated polyether.
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Comparative example 4:
the high-performance flame-retardant silane modified polyether sealant is different from the sealant in the embodiment 1 in that: the modified polysiloxane-terminated polyether is replaced by a trimethoxy-terminated polyether.
The preparation of a high performance flame retardant silane modified polyether sealant was the same as in example 1.
Test example 1:
1. measurement of acid value
The acid value of the sample was determined with reference to the method of the experiment in the standard GB/T8146-. 2g of the sample to be tested was weighed into a 250mL Erlenmeyer flask, and dissolved in 50mL of absolute ethanol, and titrated with phenolphthalein indicator using 0.5M potassium hydroxide standard solution until the solution becomes reddish and fadeless for 30 s. The results were calculated by the following formula:
AS＝56.1×C×(VS-V0)/m
in the formula, AS-acid number of sample, mg/g; c, concentration of standard alkali liquor, mol/L; v0-volume of lye consumed for titration of the blank, mL; vS-the volume of lye consumed by titration of the sample, mL; m-weight the mass of the sample, g.
2. Determination of the conversion
The acid value of D-A continuously increases with time during the addition reaction. To facilitate the determination of the conversion rate of the reaction, samples were taken at different times, at different temperatures, etc. to determine the acid value. The change in conversion is reflected laterally by the change in acid value. Accurately weighing 5g of sample, adding 30mL of 80% ethanol solution, and shaking to completely dissolve the sample. Dropwise adding phenolphthalein, and titrating with 0.2M KOH standard solution until the reaction is finished; blank tests were performed in the same manner. The conversion was calculated according to the following formula:
conversion Y ═ ASO-AS1)/(ASO-AL)×100％
In the formula, Y represents the conversion of the sample,%; a. theSO-pinocembrin acid value, mgKOH/g; a. theS1Acid value of maleopimaric acid anhydride, mgKOH/g; a. theLTheoretical acid value of maleopimaric acid anhydride, mgKOH/g.
3. Infrared Spectrometry (FT-IR)
After a sample is subjected to water removal treatment in a constant-temperature drying oven, a small amount of sample and potassium bromide are uniformly mixed in an agate mortar, ground and tabletted, and then the mixture is placed on a TENSOR 27 type infrared spectrometer for testing, wherein the scanning wave number range is 4000-500 cm-1Scanning resolution of 6cm-1The number of scans was 18.
The above tests were carried out on the polysiloxane and the modified polysiloxane obtained in example 1, and the results are shown in FIG. 1. As can be seen from the figure, 1423cm in the polysiloxane spectrum-1The absorption peak of the amino group-containing compound at 1267cm is determined by the following formula-1Is treated with a polysiloxane segmentMiddle Si-C bond absorption peak, 1096cm-1And 1023cm-1Is an absorption peak of Si-O-Si bonds in a polysiloxane chain segment; in the spectrum after modification, 3480cm is compared with that before modification-1Is characterized by the characteristic peak of hydroxyl in maleic pine tuckahoe new anhydride, 2900cm-1And 2821cm-1The absorption peak is the absorption peak of methyl and methylene in the maleic pine tuckahoe new anhydride; 1693cm in length-1The vicinity is a characteristic peak of unsaturated carbon-hydrogen bonds; 1779cm-1And 1739cm-1The characteristic absorption peak of the imide is 1423cm at the same time-1The absorption peak of (a) was retained, indicating that an amino group was retained. The above results show the success of the maleopimaric anhydride modified polysiloxane.
4. Thermogravimetric analysis (TG)
Thermal stability analysis was performed using TGAR 5000IR from TA USA. In the experiment, the mass of the sample is about 10mg, the airflow rate is 20mL/min under the condition of nitrogen atmosphere, the heating rate is 20 ℃/min, and the temperature is raised to 900 ℃ at most.
The above tests were performed on the sealants prepared in comparative example 1 and example 1, and the results are shown in FIG. 2. As can be seen from the analysis of the figure, the thermal decomposition of the sealant is divided into two stages, the mass loss of the first stage is 34-40%, and the mass loss of the second stage is about 19-23%. The thermal decomposition temperature of the sealant prepared in the example 1 is about 500 ℃ in the first stage and is obviously higher than 390 ℃ in the comparative example 1, and the thermal decomposition temperature of the sealant in the second stage is about 800 ℃ and is higher than 720 ℃ in the comparative example 1; the results show that the maleopimaric acid anhydride modified polysiloxane can effectively improve the heat resistance of the sealant, and the sealant prepared by the invention has excellent high-temperature resistance.
Test example 2:
test for flame retardancy
The oxygen index and UL94 vertical burning grade test method refers to GB/T10707 standard; wherein the oxygen index measurement sample size is 80 mm. times.7 mm. times.3 mm. UL94 vertical burning rating test: samples were allowed to stand at 23 ℃ and 50% RH for 48h before testing. Using a small sample with the length of 127mm, the width of 12.7mm and the maximum thickness of 12.7 mm; in a non-ventilated test chamber. The upper end of the sample (6.4 mm) was clamped with a clamp on the holder and the longitudinal axis of the sample was held vertically. The lower end of the sample was spaced 9.5mm from the lamp tip and 305mm from the surface of the dried absorbent cotton. The results of the above tests on the samples prepared in comparative examples 1 to 4 and examples 1 to 7 are shown in Table 1.
TABLE 1 flame retardancy test results
| Sample (I) | Limiting oxygen index | UL94 |
| Comparative example 1 | 30 | V1 |
| Comparative example 2 | 32 | V1 |
| Comparative example 3 | 31 | V1 |
| Comparative example 4 | 34 | V1 |
| Example 1 | 36 | V1 |
| Example 2 | 37 | V1 |
| Example 3 | 35 | V1 |
| Example 4 | 37 | V1 |
| Example 5 | 38 | V1 |
| Example 6 | 36 | V1 |
| Example 7 | 46 | V0 |
As can be seen from Table 1, the limited oxygen index and the UL94 grade of the sample prepared in example 1 are not significantly different from those of comparative examples 1-4, while the effect of example 7 is significantly better than that of example 1, which shows that the flame retardant performance of the sealant can be effectively improved by the synergistic effect of the addition of the magnesium orotate and the compounding of the flame retardant filler.
Test example 3:
the method for measuring the surface dry time comprises the following steps: coating a proper amount of sealant on a clean polytetrafluoroethylene plate at the temperature of (25 +/-5) DEG C and the RH of (55 +/-5)% to obtain a thickness of about 2mm, and lightly touching the surface of the sealant with fingers every 1min until the sealant is not sticky, wherein the surface drying time is the time for tack-free;
testing of curing speed
The measuring method comprises the following steps: a polytetrafluoroethylene chute with the length of about 300mm and the depth of 0-10 mm is used for gradually deepening. Extruding a proper amount of sealant into a chute, leveling by a scraper, standing at (23 + -2) deg.C and (50 + -5)% RH for 24h without bubbles in the sealant layer, peeling off the sealant film from the thinnest part to the uncured adhesive part, and measuring the depth of the groove at mm/24 h.
The tensile strength and the elongation at break were measured by the method described in GB/T528-2009, and the dumbbell-shaped standard test pieces were stretched in a tensile testing machine moving at a constant speed. The force and elongation values required for the specimen during constant stretching and when it breaks were recorded as required. The tensile strength T is calculated by the following formulas. Wherein the breaking strength Ts: stretching the sample to the maximum tensile stress in the fracture process; elongation at break δ: percent elongation at break of the test specimen. The sample preparation is a standard dumbbell sample I type, the stretching speed is 100mm/min, and the room temperature experiment is carried out.
Ts＝Fm/(ω×t)
In the formula, Ts: breaking strength, MPa; fm: maximum breaking force, N; ω: width of stenosis, mm; t: specimen thickness, mm.
Thixotropy (characterized as sag) was measured according to the method of GB/T13477.6-2018;
the hardness is measured according to the method recorded in GB/T531-2008, the sealant is injected into a circular plastic cover, the depth is 6-8 mm, the surface is finished and leveled by a scraper, and the hardness is tested by a Shore A hardness tester after the sealant is completely cured under standard conditions.
The method for measuring the storage period comprises the following steps: and (3) placing the sealing tube filled with the transparent dealcoholized sealing gum into a dark and dry environment at 25 ℃ for storage, periodically (30d) sampling, extruding and observing the appearance state of the sealing gum, and testing the mechanical properties (namely the tensile strength and the elongation at break) of the sealing gum (according to the detection experiment), wherein the critical time and the normal storage period of the sealing gum are the critical time when the appearance state and the properties are not changed much.
The test results of the sealant samples prepared in comparative examples 1-7 and comparative examples 1-4 are shown in Table 2:
TABLE 2 test results
As can be seen from the analysis in Table 2, the sealant sample prepared in example 1 has good elasticity and strength, and excellent storage stability, and each performance is obviously superior to that of comparative examples 1-4, which shows that the maleopimaric anhydride modified polysiloxane can effectively improve the mechanical property of the sealant, the surface drying time is less than 10min, the curing speed is more than 7mm/24h, the thixotropy-sag is less than 0.3mm, the hardness Shore A is 58-70, and the storage period is more than 6 months. The samples prepared in example 7 had better open time, cure speed, tensile strength and shelf life than those of example 1, indicating that the presence of magnesium orotate synergistically enhanced the above properties.
Test example 4:
viscosity test method
The determination is carried out by referring to the national standard GB/T2794-2013 method for determining the viscosity of the adhesive by a single-cylinder rotational viscometer method. Using a rotational viscometer method: (1) putting a prepolymer to be tested into a glass beaker, placing the glass beaker into a constant-temperature oil bath pot, stirring and heating the glass beaker at an electric constant speed of 200r/min for a set time; (2) and selecting a proper rotor according to the viscosity of the prepolymer, installing the rotor according to the specification of the viscometer, starting the rotor, keeping the reading constant, and recording the obtained data.
Test of Corrosion resistance
The test method was carried out with reference to HB5273-93, with a dipping depth of 40 mm. The medium is 5% hydrochloric acid aqueous solution and 5% sodium hydroxide aqueous solution. Sealing and soaking the reagent bottle with the plug, and preserving heat for 7 days in water bath at 60 ℃. After the test, the samples were observed for changes and related property changes. The test adopts the tensile strength reduction value after soaking to represent the corrosion resistance of the sample, and the test method is the same as that of test example 3.
The test results of the sealant samples prepared in comparative examples 1-4 and examples 1-7 are shown in Table 3:
table 3 viscosity and corrosion resistance test results
As can be seen from Table 3, the peel strength of the sealant sample prepared in example 1 is obviously higher than that of comparative examples 1-4, and the effect of example 7 is equivalent to that of example 1, which shows that the maleopimaric acid anhydride modified polysiloxane can effectively improve the adhesive property of the sealant; the tensile strength reduction rate of the sealant sample prepared in the example 7 is obviously lower than that of the sealant sample prepared in the example 1, and the effect of the example 1 is not obviously different from that of the comparative examples 1-4, which shows that the corrosion resistance of the sealant can be effectively improved by adding the magnesium orotate.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A preparation method of a high-performance flame-retardant silane modified polyether sealant comprises the following steps:
s1: mixing modified polysiloxane end-capped polyether, a plasticizer, a water removing agent, calcium carbonate, white carbon black and a flame-retardant filler to obtain a product A;
s2: mixing the product A obtained in the step S1 with a tackifier and a water removing agent, and adding an organic chelated tin catalyst and the water removing agent for reaction; performing vacuum defoaming treatment, stirring, discharging and sealing to obtain the sealant;
the modified polysiloxane is prepared by modifying maleopimaric acid anhydride; the maleic anhydride is prepared from maleic anhydride and pinosylvic acid in a reaction manner, wherein the molar ratio of the maleic anhydride to the pinosylvic acid is (2-2.5): 1, the reaction temperature is 260-270 ℃;
the modified polysiloxane raw material components comprise, by weight, 10-14 parts of maleopimaric acid anhydride and 40-50 parts of polysiloxane.
2. The preparation method of the high-performance flame-retardant silane-modified polyether sealant according to claim 1, characterized by comprising the following steps: the specific preparation method of the maleic pine umbellate pore-forming new anhydride comprises the following steps: taking pinocembrin acid, heating and preserving heat for a period of time under the protection of nitrogen; slowly adding maleic anhydride for reaction; and cooling in ice water, crushing, washing, drying, dissolving in glacial acetic acid, heating for refluxing, recrystallizing, washing and drying to obtain the product.
3. The preparation method of the high-performance flame-retardant silane-modified polyether sealant according to claim 1, characterized by comprising the following steps: the raw material components of the polysiloxane comprise, by weight, 10-12 parts of aminosilane, 90-95 parts of octamethylcyclotetrasiloxane, 0.4-0.6 part of hexamethyldisiloxane and 0.1-0.2 part of potassium hydroxide.
4. The preparation method of the high-performance flame-retardant silane-modified polyether sealant according to claim 1, characterized by comprising the following steps: the preparation method of the modified polysiloxane comprises the following steps: and (3) reacting the maleic pine umbellate neo-anhydride and polysiloxane for 4-5 hours at the temperature of 90-98 ℃ to obtain the modified polysiloxane.
5. A high-performance flame-retardant silane-modified polyether sealant comprising the modified polysiloxane-terminated polyether described in claim 4, wherein the apparent viscosity of the polyether is 9000 to 15000 mPas.
6. The high-performance flame-retardant silane-modified polyether sealant according to claim 5, characterized in that: the sealant comprises the following raw materials: the flame-retardant modified polysiloxane modified polyether comprises, by weight, 90-120 parts of modified polysiloxane terminated polyether, 90-110 parts of active nano calcium carbonate, 12-36 parts of polypropylene glycol, 10-26 parts of flame-retardant filler, 10-14 parts of white carbon black, 2-4 parts of vinyl trimethoxy silane, 1-3 parts of diamino silane and 0.1-0.8 part of organic chelated tin catalyst.
7. The high-performance flame-retardant silane-modified polyether sealant according to claim 6, characterized in that: the flame-retardant filler is prepared by uniformly dispersing magnesium orotate and an intumescent flame retardant, wherein the mass ratio of the magnesium orotate to the intumescent flame retardant is 1: 1.5 to 8.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025416A (en) * | 1995-05-12 | 2000-02-15 | Henkel Teroson Gmbh | Two-component adhesive/sealing mass with high initial adhesiveness |
| CN102660214A (en) * | 2012-04-06 | 2012-09-12 | 江苏天辰硅材料有限公司 | Monocomponent flame-retardant silane modified polyether sealant and preparation method thereof |
| CN104497579A (en) * | 2014-12-25 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | One-component room temperature vulcanized organic silicon rubber with high adhesion and preparation method thereof |
| CN106833478A (en) * | 2016-12-30 | 2017-06-13 | 北京华腾新材料股份有限公司 | A kind of high-performance refractory type double-component silane modified polyether seal glue and preparation method |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN110423353A (en) * | 2019-08-14 | 2019-11-08 | 中国林业科学研究院林产化学工业研究所 | A kind of polysiloxanes, maleopimaric acid modified polyorganosiloxane and maleopimaric acid modified polyorganosiloxane resistance combustion polyurethane foam |
-
2021
- 2021-01-13 CN CN202110043073.9A patent/CN112852381B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025416A (en) * | 1995-05-12 | 2000-02-15 | Henkel Teroson Gmbh | Two-component adhesive/sealing mass with high initial adhesiveness |
| CN102660214A (en) * | 2012-04-06 | 2012-09-12 | 江苏天辰硅材料有限公司 | Monocomponent flame-retardant silane modified polyether sealant and preparation method thereof |
| CN104497579A (en) * | 2014-12-25 | 2015-04-08 | 中国林业科学研究院林产化学工业研究所 | One-component room temperature vulcanized organic silicon rubber with high adhesion and preparation method thereof |
| CN106833478A (en) * | 2016-12-30 | 2017-06-13 | 北京华腾新材料股份有限公司 | A kind of high-performance refractory type double-component silane modified polyether seal glue and preparation method |
| CN110078909A (en) * | 2019-04-28 | 2019-08-02 | 上海元业体育科技有限公司 | A kind of phosphorous silane-terminated polyether and preparation method thereof |
| CN110423353A (en) * | 2019-08-14 | 2019-11-08 | 中国林业科学研究院林产化学工业研究所 | A kind of polysiloxanes, maleopimaric acid modified polyorganosiloxane and maleopimaric acid modified polyorganosiloxane resistance combustion polyurethane foam |
Non-Patent Citations (1)
| Title |
|---|
| 《马来松香改性乙烯基聚硅氧烷的合成及其性能研究》;徐涛;《化工新型材料》;20160115;46-48、51 * |
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