CN112538245B - Daylighting tile resin and preparation method thereof - Google Patents
Daylighting tile resin and preparation method thereof Download PDFInfo
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- CN112538245B CN112538245B CN202011420117.7A CN202011420117A CN112538245B CN 112538245 B CN112538245 B CN 112538245B CN 202011420117 A CN202011420117 A CN 202011420117A CN 112538245 B CN112538245 B CN 112538245B
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- flame retardant
- lighting tile
- tile resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6958—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a lighting tile resin and a preparation method thereof, belonging to the technical field of synthetic resin. The preparation raw materials of the lighting tile resin disclosed by the invention comprise a nitrogen flame retardant, a phosphorus flame retardant and a silicon flame retardant. The three flame retardants act synergistically to form a silica protective layer in the combustion process of the material, so that the stability of the carbon layer is improved, meanwhile, the material absorbs heat and cools, and releases non-combustible gas to dilute the combustible gas, thereby further improving the flame retardant efficiency.
Description
Technical Field
The invention belongs to the technical field of synthetic resin, and particularly relates to a lighting tile resin and a preparation method thereof.
Background
The lighting tile has good heat preservation and impact resistance, lighting light is in a light scattering shape, the light is soft, the light transmittance is high, most ultraviolet rays can be effectively blocked, and meanwhile, the lighting tile has good corrosion resistance and is suitable for roofs of chemical workshops. However, chemical engineering workshops are high-risk places, and once combustion or explosion occurs, the scene is difficult to control, so that the fire resistance of the lighting tiles is high, and further research on the unsaturated polyester resin for the lighting tiles is needed to improve the fire resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lighting tile resin with better flame retardant property and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the lighting tile resin is characterized in that the preparation raw materials of the lighting tile resin comprise a nitrogen flame retardant, a phosphorus flame retardant and a silicon flame retardant; the phosphorus flame retardant comprises 2-carboxyethyl phenyl hypophosphorous acid and allyl diethyl phosphate.
The action mechanism of the phosphorus flame retardant is that the pyrolysis product of the phosphorus-containing compound has strong dehydration effect, so that the polymer surface covered by the compound is carbonized to form a carbon film, thereby preventing the combustion from proceeding. The nitrogen-based flame retardant absorbs heat mainly by decomposition and generates a non-combustible gas (CO) 2 、NH 3 、N 2 Etc.), the concentration of combustible gas is diluted, thereby preventing combustion from deepening. The action mechanism of the silicon flame retardant is that the silicon flame retardant has good smoke suppression performance by promoting carbon formation and improving the structure of a carbon layer.
Preferably, the preparation raw materials of the lighting tile resin comprise the following components in parts by weight: 130-170 parts of nitrogen flame retardant, 200-230 parts of 2-carboxyethyl phenyl hypophosphorous acid, 55-120 parts of allyl diethyl phosphate and 100-120 parts of silicon flame retardant.
When the lighting tile resin is prepared, the fire retardant is added according to the proportion, the OI value can reach 28 percent, and when the proportion deviates from the proportion, the fire retardant performance is obviously reduced.
Further preferably, the preparation raw materials of the daylighting tile resin comprise the following components in parts by weight: 150 parts of nitrogen flame retardant, 214 parts of 2-carboxyethyl phenyl hypophosphorous acid, 125 parts of allyl diethyl phosphate and 108 parts of silicon flame retardant.
Preferably, the nitrogen-based flame retardant is melamine cyanurate, and the silicon-based flame retardant is diphenyl dihydroxyl silane.
Preferably, the raw materials for preparing the daylighting tile resin further comprise thermoplastic polyester, dihydric alcohol, a catalyst, acid anhydride, a stabilizer, a polymerization inhibitor and a crosslinking agent.
Preferably, the thermoplastic polyester is polyethylene terephthalate, the dihydric alcohol is methyl propylene glycol and propylene glycol, the catalyst is monobutyl tin oxide, the anhydride is maleic anhydride, the stabilizer is triphenyl phosphite, the polymerization inhibitor is methyl hydroquinone and tert-butyl hydroquinone, and the crosslinking agent is styrene.
Preferably, the preparation raw materials of the daylighting tile resin further comprise the following components in parts by weight: 450-500 parts of polyethylene terephthalate, 240-260 parts of methyl propylene glycol, 90-100 parts of propylene glycol, 0.45-0.5 part of monobutyl tin oxide, 330-365 parts of maleic anhydride, 2.3-3.2 parts of triphenyl phosphite, 0.1-0.16 part of methyl hydroquinone, 685-860 parts of styrene and 0.08-0.14 part of tert-butyl hydroquinone.
Preferably, the lighting tile resin comprises the following raw materials in parts by weight: 480 parts of polyethylene terephthalate, 250 parts of methyl propylene glycol, 95 parts of propylene glycol, 0.5 part of monobutyl tin oxide, 348 parts of maleic anhydride, 2.3 parts of triphenyl phosphite, 0.1 part of methyl hydroquinone, 727 parts of styrene and 0.1 part of tert-butyl hydroquinone.
Meanwhile, the invention discloses a preparation method of the daylighting tile resin, which comprises the following steps:
(1) Adding thermoplastic polyester, dihydric alcohol, a catalyst and a silicon flame retardant into a container, heating to 200-210 ℃, and then preserving heat;
(2) After the step (1) is finished, cooling to 100-110 ℃, adding anhydride, 2-carboxyethyl phenyl hypophosphorous acid and a stabilizer into the container in the step (1), heating to 200-210 ℃, and then preserving heat;
(3) After the step (2) is finished, cooling to 100-110 ℃, and adding a nitrogen flame retardant and methyl hydroquinone into the container in the step (2);
(4) And (4) after the step (3) is finished, adding a cross-linking agent, diethyl allyl phosphate and tert-butyl hydroquinone into the container in the step (3), and uniformly stirring to obtain the daylighting tile resin.
Preferably, the heat preservation time in the step (1) and the step (2) is 2.5-3.5h.
Compared with the prior art, the invention has the beneficial effects that: through the synergistic effect of the phosphorus flame retardant, the nitrogen flame retardant and the silicon flame retardant, the material forms a silicon dioxide protective layer in the combustion process, so that the stability of the carbon layer is improved, meanwhile, the material absorbs heat and cools, and releases non-combustible gas to dilute the combustible gas, thereby further improving the flame retardant efficiency.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Examples 1 to 5 are the daylighting tile resin of the present invention, the formulation of which is shown in table 1, and the preparation method is as follows:
(1) Adding polyethylene terephthalate, methyl propylene glycol, diphenyl dihydroxy silane and monobutyl tin oxide into a reaction kettle, heating to 200-205 ℃, and then preserving heat for 3 hours.
(2) After the step (1) is finished, cooling to 100-105 ℃, adding maleic anhydride, 2-carboxyethyl phenyl hypophosphorous acid and triphenyl phosphite into the reaction kettle, and heating to 200-205 ℃.
(3) After the step (2) is finished, cooling to 100-105 ℃, and adding melamine cyanurate and methyl hydroquinone into the reaction kettle.
(4) And (3) after the step (3) is finished, adding styrene, diethyl allylphosphate and tert-butylhydroquinone into the reaction kettle, and uniformly stirring to obtain the flame-retardant unsaturated polyester resin.
TABLE 1 examples 1-5 formulations (parts by weight)
The flame retardants in comparative examples 1 to 3 are two of phosphorus flame retardants, silicon flame retardants and nitrogen flame retardants, wherein in comparative example 1, melamine cyanurate is not present, the amount of allyl diethyl phosphate is 275 parts, and the remaining components are the same as in example 2; comparative example 2 was conducted without diphenyldihydroxysilane, and the amount of propylene glycol was 140 parts, the amount of styrene was 682 parts, the amount of allyl diethyl phosphate was 233 parts, and the remaining components were the same as in example 2; comparative example 3 was conducted without using diethyl allylphosphate and 2-carboxyethylphenylphosphinic acid, and the amounts of melamine cyanurate, maleic anhydride and styrene were 489 parts, 397 parts and 678 parts, respectively, and the rest of the ingredients were the same as in example 2.
Comparative examples 1 to 3 were prepared in substantially the same manner as in example 2.
And (3) testing the flame retardance: reference GB/T2406.2-2009 method for determining combustion behavior standard by oxygen index method
The oxygen index is the minimum oxygen concentration, expressed as volume percentage, that just maintains the combustion of the material when a mixture of oxygen and nitrogen is introduced at (23 + -2) deg.C. Sample preparation: for each resin set, 15 specimens of 100mm length, 10mm width and 4mm thickness were prepared, and the specimens were placed in a closed vessel at a temperature of (23. + -.2) ° C and a humidity of (50. + -.5)% with an initial oxygen concentration of 25% and an OI value was measured with reference to GB/T2406.2-2009, the results of which are shown in Table 2.
TABLE 2 results of OI value test of examples 1 to 5 and comparative examples 1 to 3
As can be seen from Table 2, the OI values of the materials in examples 1 to 5 are all high, and the materials can only undergo a combustion reaction in an oxygen-nitrogen mixed gas flow with high oxygen content, which shows that the three flame retardants in examples 1 to 5 can act synergistically, so that the flame retardance of the materials is far superior to that of a daylighting tile resin compounded by two types of flame retardants.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The lighting tile resin is characterized in that raw materials for preparing the lighting tile resin comprise a nitrogen-series flame retardant, a phosphorus-series flame retardant, a silicon-series flame retardant, thermoplastic polyester, dihydric alcohol, a catalyst, acid anhydride, a stabilizer, a polymerization inhibitor and a cross-linking agent; the phosphorus flame retardant comprises 2-carboxyethyl phenyl hypophosphorous acid and allyl diethyl phosphate; the silicon flame retardant is diphenyl dihydroxy silane; the nitrogen flame retardant is melamine cyanurate; the thermoplastic polyester is polyethylene terephthalate; the anhydride is maleic anhydride; the preparation method of the lighting tile resin comprises the following steps:
(1) Adding thermoplastic polyester, dihydric alcohol, a catalyst and a silicon flame retardant into a container, heating to 200-210 ℃, and then preserving heat;
(2) After the step (1) is finished, cooling to 100-110 ℃, adding anhydride, 2-carboxyethyl phenyl hypophosphorous acid and a stabilizer into the container in the step (1), heating to 200-210 ℃, and then preserving heat;
(3) After the step (2) is finished, cooling to 100-110 ℃, and adding a nitrogen flame retardant and a polymerization inhibitor into the container in the step (2);
(4) And (4) after the step (3) is finished, adding a cross-linking agent, allyl diethyl phosphate and a polymerization inhibitor into the container obtained in the step (3), and uniformly stirring to obtain the lighting tile resin.
2. The lighting tile resin of claim 1, wherein the raw materials for preparing the lighting tile resin comprise the following components in parts by weight: 130-170 parts of nitrogen flame retardant, 200-230 parts of 2-carboxyethyl phenyl hypophosphorous acid, 55-120 parts of allyl diethyl phosphate and 100-120 parts of silicon flame retardant.
3. The lighting tile resin of claim 1, wherein the raw materials for preparing the lighting tile resin comprise the following components in parts by weight: 150 parts of nitrogen flame retardant, 214 parts of 2-carboxyethyl phenyl hypophosphorous acid, 125 parts of allyl diethyl phosphate and 108 parts of silicon flame retardant.
4. A lighting tile resin as recited in claim 1, wherein said diols are methyl propylene glycol and propylene glycol, said catalyst is monobutyl tin oxide, said stabilizer is triphenyl phosphite, said polymerization inhibitor is methyl hydroquinone and t-butyl hydroquinone, said polymerization inhibitor in step (3) is methyl hydroquinone, said polymerization inhibitor in step (4) is t-butyl hydroquinone, and said cross-linking agent is styrene.
5. The lighting tile resin of claim 4, wherein the raw materials for preparing the lighting tile resin further comprise the following components in parts by weight: 450-500 parts of polyethylene terephthalate, 240-260 parts of methyl propylene glycol, 90-100 parts of propylene glycol, 0.45-0.5 part of monobutyl tin oxide, 330-365 parts of maleic anhydride, 2.3-3.2 parts of triphenyl phosphite, 0.1-0.16 part of methyl hydroquinone, 685-860 parts of styrene and 0.08-0.14 part of tert-butyl hydroquinone.
6. The lighting tile resin of claim 5, wherein the raw materials for preparing the lighting tile resin further comprise the following components in parts by weight: 480 parts of polyethylene terephthalate, 250 parts of methyl propylene glycol, 95 parts of propylene glycol, 0.5 part of monobutyl tin oxide, 348 parts of maleic anhydride, 2.3 parts of triphenyl phosphite, 0.1 part of methyl hydroquinone, 727 parts of styrene and 0.1 part of tert-butyl hydroquinone.
7. A method for preparing the daylighting tile resin according to any one of claims 4-6, comprising the following steps:
(1) Adding thermoplastic polyester, dihydric alcohol, a catalyst and a silicon flame retardant into a container, heating to 200-210 ℃, and then preserving heat;
(2) After the step (1) is finished, cooling to 100-110 ℃, adding anhydride, 2-carboxyethyl phenyl hypophosphorous acid and a stabilizer into the container in the step (1), heating to 200-210 ℃, and then preserving heat;
(3) After the step (2) is finished, cooling to 100-110 ℃, and adding a nitrogen flame retardant and methyl hydroquinone into the container in the step (2);
(4) And (4) after the step (3) is finished, adding a cross-linking agent, diethyl allyl phosphate and tert-butyl hydroquinone into the container in the step (3), and uniformly stirring to obtain the daylighting tile resin.
8. A method for preparing a lighting tile resin as claimed in claim 7, wherein the time for maintaining the temperature in steps (1) and (2) is 2.5-3.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011420117.7A CN112538245B (en) | 2020-12-04 | 2020-12-04 | Daylighting tile resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011420117.7A CN112538245B (en) | 2020-12-04 | 2020-12-04 | Daylighting tile resin and preparation method thereof |
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| CN112538245A CN112538245A (en) | 2021-03-23 |
| CN112538245B true CN112538245B (en) | 2022-11-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1239474A (en) * | 1967-07-11 | 1971-07-14 | ||
| CN101759947A (en) * | 2009-12-29 | 2010-06-30 | 浙江天和树脂有限公司 | Flame-retardant type unsaturated polyester resin and preparation method thereof |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102174177A (en) * | 2011-03-07 | 2011-09-07 | 上海新天和树脂有限公司 | Unsaturated polyester resin for high-yellowing-resistant fiber-reinforced lighting panel and preparation method thereof |
| CN102181015B (en) * | 2011-04-08 | 2013-05-01 | 四川东材科技集团股份有限公司 | Method for synthesizing reactive halogen-free flame-retardant unsaturated polyester resin |
| CN102634017B (en) * | 2012-04-13 | 2013-09-25 | 浙江华亿工程设计有限公司 | Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof |
| CN103387661A (en) * | 2013-07-22 | 2013-11-13 | 南通天和树脂有限公司 | Phosphorus-series reaction-type flame-retardant unsaturated polyester resin |
| CN104327462A (en) * | 2013-07-22 | 2015-02-04 | 于桂菊 | Phosphorus-based synergistically flame-retardant PET/PBS alloy material and preparation method thereof |
| CN107903589A (en) * | 2017-10-31 | 2018-04-13 | 杭州立心新材料有限公司 | A kind of Halogen synergistic flame-retardant PBT material with high glow-wire and preparation method thereof |
| CN108587057A (en) * | 2018-04-10 | 2018-09-28 | 安徽宏志建材科技有限公司 | A kind of daylighting weather-resistant composite, plane skylight and preparation method thereof |
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- 2020-12-04 CN CN202011420117.7A patent/CN112538245B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1239474A (en) * | 1967-07-11 | 1971-07-14 | ||
| CN101759947A (en) * | 2009-12-29 | 2010-06-30 | 浙江天和树脂有限公司 | Flame-retardant type unsaturated polyester resin and preparation method thereof |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
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| CN112538245A (en) | 2021-03-23 |
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