Lighting resin, preparation method and application thereof

Abstract

The application relates to a light-collecting resin and a preparation method and application thereof, and belongs to the technical field of light-collecting unsaturated polyester resin. The light-collecting resin comprises the following components: ethylene glycol, benzoic acid, phthalic anhydride, maleic anhydride, an antioxidant, a defoaming agent, a surfactant, a stabilizer, styrene, a solvent, a first, a second and a third polymerization inhibitor; the alcohol acid ratio is 1.03-1.13:1; the molar ratio of unsaturated acid to saturated acid is 2.5-3.5:1; the mass ratio of benzoic acid to the surfactant is 26.8-44:1; the preparation steps are as follows: 1) reacting ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, an antioxidant and the first polymerization inhibitor; 2) after the reaction is completed, the temperature is increased and kept; 3) the second polymerization inhibitor is added after temperature reduction, and the third polymerization inhibitor, a crosslinking agent, the surfactant and the defoaming agent are added after temperature reduction, and the solvent is added to obtain the light-collecting resin. In the application, the surfactant and the benzoic acid are synergistic, and the compatibility of the polyester and the crosslinking agent is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of light-gathering unsaturated polyester resin, and particularly relates to a light-gathering resin as well as a preparation method and application thereof. BACKGROUND

[0002] A large amount of symmetrical diols, such as ethylene glycol, is commonly used in the synthesis formula of light-gathering unsaturated polyester resin, which easily causes poor compatibility of the polyester and the crosslinking agent in the resin dilution stage; in the production field of light-gathering resin, the compatibility of the polyester and the crosslinking agent is one of the key factors determining the performance of the product. For a long time, benzoic acid is generally used in the industry to improve the compatibility of the two. However, this traditional method has obvious disadvantages. In the reaction process of the light-gathering resin, benzoic acid will sublimate in the later stage of the reaction due to heating, and a large amount of sublimated benzoic acid vapor is easy to condense in the pipeline, thereby blocking the pipeline system. This not only seriously affects the continuity of production, but also greatly increases the labor cost and equipment loss due to frequent pipeline cleaning and maintenance.

[0003] In Chinese Invention Patent with the title of "Saturated Polyester Resin and Preparation Method Thereof", "Publication No. CN115215970A", the compatibility of the unsaturated polyester and the crosslinking agent is improved by adding isobutyl alcohol in the formula, and the use of benzoic acid is completely abandoned. Isobutyl alcohol can effectively reduce the surface tension between the polyester and the crosslinking agent due to its unique molecular structure, thereby achieving good compatibility effect. However, in actual production, the raw material price of isobutyl alcohol is about 8100 yuan / ton, while the raw material price of national standard benzoic acid is only 7000 yuan / ton, and the price of isobutyl alcohol per ton is 1100 yuan higher than that of benzoic acid. If the conventional addition ratio of isobutyl alcohol and benzoic acid in the production formula of light-gathering resin is calculated, the cost of 33~55 yuan per ton of light-gathering resin produced by using isobutyl alcohol will be increased only in the raw material of the compatibilizer. This does not take into account the additional cost of special protection measures due to the flammable nature of isobutyl alcohol during storage and transportation.

[0004] In the fierce market competition environment, the price sensitivity of light-gathering resin is extremely high, and the downstream application fields such as building light-gathering plate and greenhouse covering material pay great attention to the product price. The cost increase caused by the use of isobutyl alcohol makes the produced light-gathering resin lose the price advantage in the market and greatly reduces the cost performance.

[0005] Therefore, how to effectively control the production cost while ensuring good compatibility of the polyester and the crosslinking agent in the light-gathering resin has become a problem to be solved in the industry. SUMMARY

[0006] The technical problem to be solved by the present application is to overcome the shortcomings of the prior art and provide a light-gathering resin as well as a preparation method and application thereof. The present application improves the compatibility of the polyester and the crosslinking agent through the synergistic effect of the surfactant and benzoic acid.

[0007] In order to achieve the above-mentioned purpose, the present application provides a light collecting resin, comprising the following components in parts by weight: ethylene glycol 20-442 parts, benzoic acid 34-43 parts, phthalic anhydride 102-105 parts, maleic anhydride 240-246 parts, antioxidant 0.4-0.5 parts, first polymerization inhibitor 0.01-0.05 parts, second polymerization inhibitor 0.05-0.08 parts, third polymerization inhibitor 0.01-0.03 parts, defoaming agent 0.97-1.05 parts, surfactant 0.95-1.05 parts, stabilizer 0.01-0.03 parts, crosslinking agent 230-250 parts, solvent 85-125 parts; the molar ratio of alcohol to acid is 1.03-1.13:1, the molar ratio of total alcohol to total acid is referred to as alcohol acid ratio; the molar ratio of unsaturated acid to saturated acid is 2.5-3.5:1; the mass ratio of benzoic acid to surfactant is 26.8-44:1, which improves the comprehensive performance of the resin by optimizing the synergistic effect of the components. The light collecting resin of the present application has good compatibility, low raw material price, and can effectively control the production cost.

[0008] The first polymerization inhibitor, the second polymerization inhibitor, and the third polymerization inhibitor are at least one of methylhydroquinone, hydroquinone, and 4-tert-butylcatechol; the first polymerization inhibitor, the second polymerization inhibitor, and the third polymerization inhibitor are the same or different, the first polymerization inhibitor is added in the pre-polymerization and temperature rising stage, which needs to play an initial inhibition effect at medium-high temperature to prevent the reaction from running out of control too early; the second polymerization inhibitor further blocks the residual free radical activity at the initial stage of cooling to prevent side reactions. The third polymerization inhibitor stabilizes the system at low temperature to avoid slow self-polymerization during storage or subsequent processing.

[0009] The weight ratio of the first polymerization inhibitor, the second polymerization inhibitor, and the third polymerization inhibitor is 1:1-8:0.2-2. This ratio allows the three polymerization inhibitors to synergistically act in their respective temperature intervals, meeting the polymerization inhibition requirements throughout the reaction process. This ratio can regulate the polymerization inhibition intensity at each stage, ensuring that the reaction process is controllable and does not interfere with the final crosslinking and curing, ensuring that the performance of the light collecting resin meets the standards.

[0010] The components further include, by weight, 30.8-31.2 parts of diethylene glycol, 27.8-28.2 parts of propylene glycol, and 12.8-13.2 parts of glycerol. Preferably, 31 parts of diethylene glycol, 28 parts of propylene glycol, and 13 parts of glycerol. The two hydroxyl groups in the diethylene glycol molecule can participate in the esterification reaction of the resin, introducing a flexible ether bond structure. This structure can increase the flexibility of the resin molecular chain, improve the toughness and impact resistance of the resin. The propylene glycol participates in the esterification reaction to control the degree of branching and crosslinking density of the resin, which can balance the rigidity and flexibility of the resin to a certain extent, ensuring that the resin has sufficient mechanical strength and avoiding the brittleness problem caused by excessive rigidity. Glycerol is a trihydric alcohol, and the presence of three hydroxyl groups in the molecule makes it act as a crosslinking point in the reaction, increasing the branching degree and crosslinking density of the resin. This helps to improve the heat resistance, mechanical strength, and weather resistance of the resin.

[0011] The ethylene glycol includes 20-241 parts of crude ethylene glycol with a content of 60%-88% and 0-200 parts of distilled ethylene glycol with a content of 88%-95%. The use of crude ethylene glycol with a content of 60%-88% and distilled ethylene glycol with a content of 88%-95% reduces the cost, and the use of non-standard propylene glycol improves the compatibility.

[0012] The crude ethylene glycol with a content of 60%-88% is purchased from Hebei Fengyi Chemical Product Co., Ltd., and the content is detected using a Shimadzu GC-2014C gas chromatograph at a column temperature of 180°C with a 0.1-microliter sample.

[0013] The antioxidant is at least one of triphenyl phosphite and 2,6-di-tert-butyl-p-methylphenol. As a hindered phenolic antioxidant, 2,6-di-tert-butyl-p-methylphenol can capture free radicals in the oxidation chain reaction, blocking the aging process of the material. Triphenyl phosphite can effectively inhibit oxidative decomposition, prevent material brittleness and transparency loss, and perform excellently especially in high-temperature processing environments.

[0014] The defoaming agent is model UP11; the defoaming agent can inhibit the foam generated by gas release or stirring during the reaction process, avoiding the influence of volume expansion on mass transfer efficiency and equipment operation stability.

[0015] The stabilizer is at least one of 8% copper naphthenate and 5% copper naphthenate; 8% copper naphthenate indicates that the mass percentage of copper content is 8%; 5% copper naphthenate indicates that the mass percentage of copper content is 5%; the stabilizer can inhibit thermal degradation of the resin, preventing molecular chain rupture or color deepening.

[0016] The crosslinking agent is styrene; the crosslinking agent introduces chemical bonds, promotes linear molecular chains to form a three-dimensional network structure, and improves the mechanical strength and solvent resistance of the resin.

[0017] The surface active agent is at least one of a silane coupling agent, a polyether, and a sorbitan fatty acid ester. The silane coupling agent is gamma-methacryloxypropyl trimethoxysilane, abbreviated as KH-570; the polyether is polyethylene glycol 400; and the sorbitan fatty acid ester is sorbitan oleate, abbreviated as Span 80. The surface active agent has the functions of dispersion and wetting, can reduce the interfacial tension between the resin and the solvent, promote the uniform dispersion of the crosslinking agent, the polymerization inhibitor and other components, and avoid local aggregation to cause uneven performance.

[0018] The benzoic acid in the application can undergo esterification with the free hydroxyl groups at the ends of the polyester to generate benzoic acid ester bonds, reduces the polarity of the polyester molecules, makes the properties of the polyester and the crosslinking agent more similar, and thus enhances the compatibility of the two; and the surface active agent reduces the interfacial tension between the polyester and the crosslinking agent, weakens the repulsive force between the molecules of the two, and promotes the interaction between the molecules. The surface active agent and the benzoic acid synergistically improve the compatibility of the polyester and the crosslinking agent, make the resin system have stability and uniformity, and avoid the phase separation of the resin.

[0019] The solvent is at least one of dichloroethane and dichloropropane. The solvent dilutes the resin system, reduces the processing viscosity, and facilitates subsequent coating or injection molding.

[0020] The application also provides a preparation method of the light harvesting resin.

[0021] (1) ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, an antioxidant and a first polymerization inhibitor are added into a reaction container, the temperature is raised, and a prepolymerization reaction is performed for 0.5-2 h;

[0022] (2) after the prepolymerization reaction is completed, the temperature is raised to 200-204 ℃, and the temperature is kept for 0.5-2 h until the acid value is 28.2-32.6 mg / KOH and the cone and plate viscosity is 490.0-528.9 mPa·s;

[0023] (3) the temperature is lowered, a second polymerization inhibitor is added, the temperature is continuously lowered, a third polymerization inhibitor, a crosslinking agent, a surface active agent, a stabilizer and a defoaming agent are added and uniformly mixed, the temperature is further lowered, and a solvent is added and uniformly mixed to obtain the light harvesting resin.

[0024] The specific operation of step (1) is to add ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, an antioxidant and a first polymerization inhibitor into a reaction container, and after water is reacted out by heating to 160-165 DEG C, a prepolymerization reaction is carried out for 0.5-2h; step (1) is heated to 160-165 DEG C under nitrogen protection, and the nitrogen protection is to physically isolate oxygen, assist in dehydration and stabilize the reaction system, so as to ensure the integrity of the molecular chain of the unsaturated polyester resin, the color stability and the process safety.

[0025] When the formula contains diethylene glycol, propylene glycol and glycerol, the specific operation of step (1) is to add diethylene glycol, propylene glycol, glycerol, ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, an antioxidant and a first polymerization inhibitor into a reaction container, and after water is reacted out by heating to 160-165 DEG C, a prepolymerization reaction is carried out for 0.5-2h.

[0026] The rate of heating in step (2) is 10-15 DEG C / h, and exceeding this range may cause local overheating or uneven mass transfer; avoiding too fast heating to cause monomers to be consumed too early or local concentration to be uneven, thereby affecting the condensation degree and the molecular weight distribution; through controllable heating, it is ensured that the esterification reaction of carboxylic acid and hydroxyl group is fully carried out, and too fast heating may inhibit the removal efficiency of carboxylic acid; the target of the cone and plate viscosity is 480-530 mPa s, and too slow heating rate may cause the reaction time to be prolonged, the viscosity to exceed the upper limit, too fast heating rate may cause local violent polymerization, uneven viscosity or excessive viscosity.

[0027] The specific operation of step (3) is to add a second polymerization inhibitor by cooling to 188-193 DEG C, and then to add a third polymerization inhibitor, a crosslinking agent, a surfactant, a stabilizer and a defoaming agent by further cooling to 150-170 DEG C and mixing uniformly; then to add a solvent by further cooling to 60-70 DEG C and mixing uniformly; to cool to ≤50 DEG C; and to obtain a daylighting resin.

[0028] According to another aspect of the present application, there is also provided an application of the above-mentioned daylighting resin or the daylighting resin prepared according to the above-mentioned preparation method in the field of daylighting tiles.

[0029] Compared with the prior art, the present application has the beneficial effects that:

[0030] 1. The surfactant in the present application synergizes with benzoic acid, improves the compatibility of the polyester and the crosslinking agent, makes the resin system have stability and uniformity, and avoids the phase separation phenomenon of the resin. The benzoic acid can esterify with the free hydroxyl group at the end of the polyester to generate a benzoic acid ester bond, reduces the polarity of the polyester molecule, makes the properties of the polyester and the crosslinking agent more similar, and thus enhances the compatibility of the two; and the surfactant reduces the interfacial tension between the polyester and the crosslinking agent, weakens the repulsive force between the molecules of the two, and promotes the interaction between the molecules.

[0031] 2. The production cost of the application is low, and the process flow is simple and clear, the required raw materials are easy to obtain, which can effectively control the production cost, and has economic feasibility and technical operability. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 Figure for the prepared light collecting resin after being frozen at -40℃ for 48h.

[0033] Figure 2 Figure for the prepared light collecting resin after being frozen at -20℃ for 24h with different contents of surfactant. DETAILED DESCRIPTION

[0034] The following will be combined with the drawings Figures 1-2 The application is further illustrated.

[0035] Example 1 is the best embodiment of the application, and the application will be further illustrated in combination with specific examples and comparative examples.

[0036] Activity = moles of unsaturated acid / total moles of saturated acid;

[0037] Actual consumption = total amount of raw materials / total actual yield;

[0038] Theoretical consumption = total amount of raw materials / (total amount of raw materials - theoretical water output).

[0039] The chemical aids used in the examples and comparative examples of the application are all commercially available, and the specific information is as follows:

[0040] Diethylene glycol: purchased from Ningbo Hongyixin Import and Export Co., Ltd.;

[0041] Non-standard propylene glycol: purchased from Hainan Hongfeier Energy Co., Ltd.;

[0042] Glycerol, also known as glycerol: purchased from Shandong Jiangze International Trade Co., Ltd.;

[0043] 60%~88% content of crude ethylene glycol: purchased from Hebei Fengyi Chemical Products Co., Ltd.;

[0044] 88%~95% content of distilled ethylene glycol: purchased from Mayton Science & Energy Co., Ltd. in Cangzhou;

[0045] Benzoic acid: purchased from Changzhou Tenghui Chemical Co., Ltd.;

[0046] Phthalic anhydride, referred to as phthalic anhydride: purchased from Zibo Yuxing Trade Co., Ltd.;

[0047] Maleic anhydride: purchased from Tianjin Dajia Chemical Co., Ltd.;

[0048] Triphenyl phosphite: purchased from Jiangsu Changqing Tree New Material Technology Co., Ltd.;

[0049] 2,6-di-tert-butyl-4-methylphenol, referred to as BHT, purchased from Changzhou Yurong Chemical Co., Ltd.

[0050] Methylhydroquinone: purchased from Changzhou Yurong Chemical Co., Ltd.

[0051] p-benzenediol: purchased from Changzhou Yurong Chemical Co., Ltd.

[0052] 4-tert-butylcatechol: purchased from Changzhou Yurong Chemical Co., Ltd.

[0053] KH-570: purchased from Quanzhou Kangjin New Material Technology Co., Ltd.

[0054] Polyethylene glycol 400: purchased from Wuxi Yatai United Chemical Co., Ltd.

[0055] Span 80: purchased from Hefei Qiansheng Biological Technology Co., Ltd.

[0056] 8% copper naphthenate: purchased from Shanghai Taoyuan Cobalt Industry Co., Ltd.

[0057] 5% copper naphthenate: purchased from Shanghai Taoyuan Cobalt Industry Co., Ltd.

[0058] The defoamer is UP11, purchased from Taizhou Tianhe Chemical Co., Ltd.

[0059] Dichloroethane: purchased from Hubei Chuansai Chemical Co., Ltd.

[0060] Dichloropropane is 1,2-dichloropropane: purchased from Huantai Fuzhong Chemical Co., Ltd.

[0061] Styrene: purchased from Shenyang Jinhua Petrochemical Co., Ltd.

[0062] Gas chromatograph GC-2014C: purchased from Wuhan Kolin Pufeng Instrument Co., Ltd.

[0063] Example 1

[0064] The formula of the light-collecting resin of this example is composed of the following components:

[0065] Maleic anhydride 245 parts, phthalic anhydride 105 parts, benzoic acid 35 parts, 95% distilled ethylene glycol 201 parts, 82% content of crude ethylene glycol 20 parts, non-standard propylene glycol 28 parts, glycerol 13 parts, first polymerization inhibitor hydroquinone 0.01 parts, antioxidant triphenyl phosphite 0.45 parts, second polymerization inhibitor hydroquinone 0.08 parts, crosslinking agent styrene 230 parts, third polymerization inhibitor 4-tert-butyl hydroquinone 0.02 parts, surfactant silane coupling agent γ-methacryloxypropyl trimethoxysilane 1.01 parts, stabilizer 8% copper naphthenate 0.01 parts, defoaming agent UP11 0.97 parts, solvent dichloroethane 120 parts;

[0066] The preparation method of the embodiment comprises the following steps:

[0067] (1) Put maleic anhydride, phthalic anhydride, benzoic acid, 95% distilled ethylene glycol, 82% content of crude ethylene glycol, non-standard propylene glycol, glycerol, first polymerization inhibitor hydroquinone and antioxidant triphenyl phosphite into a reaction container, and heat to 160°C under nitrogen protection to remove water, and then pre-polymerize for 1h;

[0068] (2) After the pre-polymerization reaction is completed, heat to 202°C at a heating rate of 13°C / h, and keep the temperature until the acid value is 32.6mg / KOH and the cone and plate viscosity is 490mPa·s;

[0069] (3) Cool to 190°C, add second polymerization inhibitor hydroquinone, continue to cool to 160°C, add third polymerization inhibitor 4-tert-butyl hydroquinone, crosslinking agent styrene, surfactant γ-methacryloxypropyl trimethoxysilane, stabilizer 8% copper naphthenate, and defoaming agent propylene glycol fatty acid ester, and mix well;

[0070] (4) Cool to 68°C again, add solvent dichloroethane, mix well, cool to ≤50°C, and obtain the daylighting resin.

[0071] Example 2

[0072] The formula of the daylighting resin of the embodiment comprises the following components:

[0073] Maleic anhydride 245 parts, phthalic anhydride 105 parts, benzoic acid 43 parts, 95% distilled ethylene glycol 181 parts, 86% content of crude ethylene glycol 45 parts, non-standard propylene glycol 28 parts, glycerol 13 parts, first polymerization inhibitor hydroquinone 0.05 parts, antioxidant 2, 6-di-tert-butyl-p-methyl phenol 0.45 parts, second polymerization inhibitor hydroquinone 0.05 parts, crosslinking agent styrene 250 parts, third polymerization inhibitor methylhydroquinone 0.02 parts, surfactant 1.03 parts, surfactant is composed of polyethylene glycol fatty acid ester and silane coupling agent γ-methacryloyloxy propyl trimethoxysilane in a weight ratio of 1:1, stabilizer 8% copper naphthenate 0.01 parts, defoamer of UP11 type 1 part, solvent dichloropropane 85 parts;

[0074] The preparation method of the embodiment comprises the following steps:

[0075] (1) Put maleic anhydride, phthalic anhydride, benzoic acid, 95% distilled ethylene glycol, 86% content of crude ethylene glycol, non-standard propylene glycol, glycerol, first polymerization inhibitor hydroquinone and antioxidant 2, 6-di-tert-butyl-4-methyl phenol into a reaction container, and heat to 165°C under nitrogen protection, and after water is discharged, pre-polymerize for 2h;

[0076] (2) After the pre-polymerization is completed, heat to 203°C at a heating rate of 12°C / h, and keep the temperature until the acid value is 31.1 mg / KOH and the cone and plate viscosity is 528.9 mPa·s;

[0077] (3) Cool to 192°C and add second polymerization inhibitor hydroquinone, continue to cool to 150°C and add third polymerization inhibitor methylhydroquinone, surfactant, stabilizer 8% copper naphthenate, defoamer polydimethylsiloxane and crosslinking agent styrene, and mix uniformly;

[0078] (4) Continue to cool to 70°C and add solvent dichloropropane, and cool to ≤50°C to obtain a daylighting resin.

[0079] Example 3

[0080] The formula of the daylighting resin of the embodiment is composed of the following components:

[0081] Maleic anhydride 240 parts, phthalic anhydride 103 parts, benzoic acid 43 parts, distilled ethylene glycol 182 parts, 82% content of crude ethylene glycol 36 parts, non-standard propylene glycol 28 parts, glycerol 13 parts, first polymerization inhibitor hydroquinone 0.05 parts, antioxidant triphenyl phosphite 0.45 parts, second polymerization inhibitor 8% copper naphthenate 0.07 parts, crosslinking agent styrene 230 parts, third polymerization inhibitor hydroquinone 0.02 parts, surfactant is silane coupling agent γ-methacryloyloxy propyl trimethoxysilane 0.97 parts, stabilizer 5% copper naphthenate 0.01 parts, defoamer of UP11 type 1.05 parts, solvent dichloropropane 125 parts.

[0082] The preparation method of the embodiment comprises the following steps:

[0083] (1) maleic anhydride, phthalic anhydride, benzoic acid, distilled ethylene glycol, 82% content of crude ethylene glycol, non-standard propylene glycol, glycerol, the first polymerization inhibitor hydroquinone and the antioxidant triphenyl phosphite are added into a reaction container, and the temperature is raised to 161°C under nitrogen protection, and after water is discharged, pre-polymerization is carried out for 1.5h;

[0084] (2) after the pre-polymerization reaction is completed, the temperature is raised to 203°C at a temperature raising rate of 10°C / h, and the temperature is kept until the acid value is 30.8mg / KOH, and the cone-plate viscosity is 510.7mPa·s;

[0085] (3) the temperature is lowered to 188°C, the second polymerization inhibitor 8% copper naphthenate is added, the temperature is continuously lowered to 160°C, the third polymerization inhibitor hydroquinone, the surfactant γ-methacryloyloxypropyl trimethoxysilane, the stabilizer 5% copper naphthenate, the defoaming agent polydimethylsiloxane and the crosslinking agent styrene are added and uniformly mixed;

[0086] (4) the temperature is continuously lowered to 65°C, the solvent dichloropropane is added, after stirring uniformly, dichloropropane is added again, the temperature is lowered to ≤50°C, and the daylight resin is obtained.

[0087] Embodiment 4

[0088] The formula of the daylight resin of the embodiment is composed of the following components:

[0089] maleic anhydride 245 parts, phthalic anhydride 105 parts, benzoic acid 35 parts, distilled ethylene glycol 182 parts, 88% content of crude ethylene glycol 46 parts, non-standard propylene glycol 28 parts, glycerol 13 parts, the first polymerization inhibitor hydroquinone 0.05 parts, the antioxidant triphenyl phosphite 0.45 parts, the second polymerization inhibitor 4-tert-butyl hydroquinone 0.07 parts, the crosslinking agent styrene 231 parts, the third polymerization inhibitor hydroquinone 0.03 parts, the surfactant 0 parts, the stabilizer 5% copper naphthenate 0.01 parts, the defoaming agent of model UP11 0.99 parts, the solvent dichloroethane 59 parts, the solvent dichloropropane 59 parts;

[0090] The preparation method of the embodiment comprises the following steps:

[0091] (1) maleic anhydride, phthalic anhydride, benzoic acid, distilled ethylene glycol, 88% content of crude ethylene glycol, non-standard propylene glycol, glycerol, the first polymerization inhibitor hydroquinone and the antioxidant triphenyl phosphite are added into a reaction container, and the temperature is raised to 163°C under nitrogen protection, and after water is discharged, pre-polymerization is carried out for 0.5h;

[0092] (2) After the prepolymerization reaction is completed, the temperature is raised to 202°C at a rate of 13°C / h, and the temperature is kept until the acid value is 28.2 mg / KOH and the cone-plate viscosity is 490.3 mPa·s;

[0093] (3) The temperature is lowered to 193°C, the second polymerization inhibitor 4-tert-butyl o-benzosemicarbazone is added, and the temperature is continuously lowered to 160°C, and the third polymerization inhibitor 4-tert-butyl o-benzosemicarbazone, the stabilizer 5% naphthenic acid copper, the defoaming agent polydimethylsiloxane, and the crosslinking agent styrene are uniformly mixed;

[0094] (4) The temperature is continuously lowered to 62°C, the solvent dichloroethane and dichloropropane are added, and after stirring, the temperature is lowered to ≤50°C to obtain the daylighting resin.

[0095] Example 5

[0096] The formula of the daylighting resin of the present embodiment is composed of the following components:

[0097] Maleic anhydride 243 parts, phthalic anhydride 104 parts, benzoic acid 35 parts, 86% content of crude ethylene glycol 241 parts, diethylene glycol 31 parts, the first polymerization inhibitor p-benzosemicarbazone 0.05 parts, the antioxidant 2,6-di-tert-butyl-p-methyl phenol 0.45 parts, the second polymerization inhibitor p-benzosemicarbazone 0.07 parts, the crosslinking agent styrene 228 parts, the third polymerization inhibitor p-benzosemicarbazone 0.01 parts, the surfactant Span 80 0.98 parts, the stabilizer 8% naphthenic acid copper 0.01 parts, the defoaming agent of type UP11 0.98 parts, and the solvent dichloroethane 117 parts;

[0098] The preparation method of the present embodiment comprises the following steps:

[0099] (1) Maleic anhydride, phthalic anhydride, benzoic acid, 86% content of crude ethylene glycol, diethylene glycol, the first polymerization inhibitor p-benzosemicarbazone, and the antioxidant 2,6-di-tert-butyl-4-methyl phenol are added to a reaction container, and the temperature is raised to 161°C under nitrogen protection, and after water is discharged, the prepolymerization reaction is carried out for 1 h;

[0100] (2) After the prepolymerization reaction is completed, the temperature is raised to 201°C at a rate of 13°C / h, and the temperature is kept until the acid value is 32.5 mg / KOH and the cone-plate viscosity is 509.4 mPa·s;

[0101] (3) The temperature is lowered to 188°C, the second polymerization inhibitor p-benzosemicarbazone is added, and the temperature is continuously lowered to 165°C, and the third polymerization inhibitor p-benzosemicarbazone, the surfactant Span 80, the stabilizer 8% naphthenic acid copper, the defoaming agent polydimethylsiloxane, and the crosslinking agent styrene are uniformly mixed;

[0102] (4) The temperature is continuously lowered to 60°C, the solvent dichloroethane is added, and after stirring, the temperature is lowered to ≤50°C to obtain the daylighting resin.

[0103] Example 6

[0104] The formula of the light resin of the embodiment is composed of the following components:

[0105] Maleic anhydride 244 parts, phthalic anhydride 104 parts, benzoic acid 35 parts, distilled ethylene glycol 155 parts, 82% content of crude ethylene glycol 70 parts, non-standard propylene glycol 28 parts, glycerol 13 parts, first polymerization inhibitor hydroquinone 0.05 parts, antioxidant 2, 6-di-tert-butyl-p-methyl phenol 0.45 parts, second polymerization inhibitor hydroquinone 0.07 parts, crosslinking agent styrene 228 parts, third polymerization inhibitor hydroquinone 0.02 parts, surfactant 0.98 parts, surfactant composed of polyethylene glycol fatty acid ester and silane coupling agent in a weight ratio of 1:1, stabilizer 5% copper naphthenate 0.01 parts, defoaming agent of type UP11 0.99 parts, solvent dichloroethane 117 parts;

[0106] The preparation method of the embodiment comprises the following steps:

[0107] (1) Put maleic anhydride, phthalic anhydride, benzoic acid, distilled ethylene glycol, 82% content of crude ethylene glycol, non-standard propylene glycol, glycerol, first polymerization inhibitor hydroquinone and antioxidant 2, 6-di-tert-butyl-4-methyl phenol into a reaction container, and heat to 161℃ under nitrogen protection, and after water is discharged, pre-polymerize for 1h;

[0108] (2) After the pre-polymerization reaction is completed, heat to 204℃ at a heating rate of 15℃ / h, and keep the temperature until the acid value is 28.6mg / KOH and the cone and plate viscosity is 506.4mPa•s;

[0109] (3) Cool to 190℃, add second polymerization inhibitor hydroquinone, continue to cool to 170℃, add third polymerization inhibitor hydroquinone, surfactant, stabilizer 5% copper naphthenate, defoaming agent propylene glycol fatty acid ester and crosslinking agent styrene, and mix uniformly;

[0110] (4) Continue to cool to 60℃, add solvent dichloroethane, stir uniformly, and then cool to ≤50℃, to obtain light resin with good compatibility.

[0111] Table 1 reaction raw materials of the embodiment

[0112] .

[0113] Comparative Example 1

[0114] The preparation method of the light resin of the comparative example is the same as that of the embodiment 1, and the only difference is that no benzoic acid is added in step (1), the amount of phthalic anhydride is increased under the condition of ensuring the same activity, and the amounts of other components are adjusted.

[0115] Comparative Example 2

[0116] The preparation method of the light collecting resin in the present comparative example is the same as that in Example 2, except that the amount of benzoic acid is increased in step (1), and the amount of phthalic anhydride is correspondingly reduced while keeping the activity unchanged, and the amounts of other components are adjusted.

[0117] Comparative Example 3

[0118] The preparation method of the light collecting resin in the present comparative example is the same as that in Example 5, except that the amount of benzoic acid is increased in step (1), and the amount of phthalic anhydride is correspondingly reduced while keeping the activity unchanged, and the amounts of other components are adjusted.

[0119] Comparative Example 4

[0120] The preparation method of the light collecting resin in the present comparative example is the same as that in Example 2, except that 30 parts of benzoic acid is added in step (1), and 1.04 parts of surfactant is added in step (3), and the surfactant is composed of polyethylene glycol fatty acid ester and silane coupling agent in a weight ratio of 1:1.

[0121] Comparative Example 5

[0122] The preparation method of the light collecting resin in the present comparative example is the same as that in Example 3, except that 122 parts of benzoic acid is added in step (1), and 1.04 parts of surfactant is added in step (3), and the surfactant is composed of 0.96 parts of silane coupling agent.

[0123] Table 2 Reaction raw materials of comparative examples

[0124] .

[0125] Performance test

[0126] The light collecting resins prepared in the examples and comparative examples were tested for performance, and the specific test results are shown in Table 3.

[0127] The tensile strength of the light collecting resin was tested in accordance with GB / T2567-2021.

[0128] The tensile elastic modulus of the light collecting resin was tested in accordance with GB / T2567-2021.

[0129] The elongation at break of the light collecting resin was tested in accordance with GB / T2567-2021.

[0130] The bending strength of the light collecting resin was tested in accordance with GB / T2567-2021.

[0131] The bending elastic modulus of the light collecting resin was tested in accordance with GB / T2567-2021.

[0132] The impact strength of the daylighting resin is tested according to GB / T2567-2021.

[0133] The heat distortion temperature of the daylighting resin is tested according to GB / T1643-2019.

[0134] The prepared daylighting resin is frozen at -40℃ for 48h, and the color of the daylighting resin is observed by visual observation; see Figure 1 , Figure 1 (a) in FIG. of Example 1 is a diagram of the daylighting resin prepared in Example 1 after being frozen at -40℃ for 48h; Figure 1 (b) in FIG. of Example 5 is a diagram of the daylighting resin prepared in Example 5 after being frozen at -40℃ for 48h; Figure 1 (c) in FIG. of Example 6 is a diagram of the daylighting resin prepared in Example 6 after being frozen at -40℃ for 48h; Figure 1 (d) in FIG. of Comparative Example 1 is a diagram of the daylighting resin prepared in Comparative Example 1 after being frozen at -40℃ for 48h; Figure 1 (d) in FIG. of Comparative Example 2 is a diagram of the daylighting resin prepared in Comparative Example 2 after being frozen at -40℃ for 48h.

[0135] The light transmittance test method is as follows: 50g of the daylighting resin prepared in the examples and comparative examples is added with accelerators and curing agents and stirred rapidly and uniformly, then poured on a plastic film, covered with two layers of daylighting glass fiber felt and a layer of film in turn, and the resin is completely and uniformly infiltrated on the glass fiber felt with a rolling knife, while ensuring the uniformity of the thickness of the plate, then placed in an 80℃ oven for 3min, the plate is taken out and cooled, and the light transmittance is observed by visual observation.

[0136] 50g of the daylighting resin is taken, different contents of surfactants are added, and the resin is frozen at -20℃ for 24h in a refrigerator, and the layering of the resin is observed by visual observation; see Figure 2 , Figure 2 (a) in FIG. of Example 4 is a diagram of the daylighting resin prepared in Example 4 after being frozen at -20℃ for 24h with 0.5% surfactant; Figure 2 (b) in FIG. of Example 4 is a diagram of the daylighting resin prepared in Example 4 after being frozen at -20℃ for 24h with 0.8% surfactant; Figure 2 (c) in FIG. of Example 4 is a diagram of the daylighting resin prepared in Example 4 after being frozen at -20℃ for 24h with 1.0% surfactant; Figure 2 (d) in FIG. of Example 4 is a diagram of the daylighting resin prepared in Example 4 after being frozen at -20℃ for 24h with 1.2% surfactant.

[0137] Table 3 Performance test results of examples and comparative examples

[0138] .

[0139] The surfactant and benzoic acid in the application have synergistic effect, which improves the compatibility of the polyester and the crosslinking agent, and makes the resin system have stability and uniformity, and avoids the phase separation of the resin.

[0140] It can be seen that, with the increase of the amount of crude alcohol, the color of the daylight resin is more yellow. The daylight resin prepared in Example 5 has a higher color because the amount of crude alcohol used is high. The comparative example 1 has a clear layered structure, and the compatibility of the polyester and the crosslinking agent is poor because it does not contain benzoic acid and surfactant. Figure 1 It can be seen that, with the increase of the amount of crude alcohol, the color of the daylight resin is more yellow. The daylight resin prepared in Example 5 has a higher color because the amount of crude alcohol used is high. The comparative example 1 has a clear layered structure, and the compatibility of the polyester and the crosslinking agent is poor because it does not contain benzoic acid and surfactant.

[0141] It can be seen that, with the increase of the amount of crude alcohol, the color of the daylight resin is more yellow. The daylight resin prepared in Example 5 has a higher color because the amount of crude alcohol used is high. The comparative example 1 has a clear layered structure, and the compatibility of the polyester and the crosslinking agent is poor because it does not contain benzoic acid and surfactant.

[0142] Figure 2 It can be seen that, with the increase of the amount of crude alcohol, the color of the daylight resin is more yellow. The daylight resin prepared in Example 5 has a higher color because the amount of crude alcohol used is high. The comparative example 1 has a clear layered structure, and the compatibility of the polyester and the crosslinking agent is poor because it does not contain benzoic acid and surfactant.

[0143] The above is only a preferred embodiment of the present application, and is not intended to limit the other forms of the present application. Any skilled person in the art can use the disclosed technical content to make changes or modifications to equivalent embodiments. However, any simple modification, equivalent change and modification made on the basis of the technical essence of the present application to the above embodiments, without departing from the technical solution of the present application, still falls within the protection scope of the present application.​

Claims

1. A light-transmitting resin, characterized in that, By weight, it comprises the following components: ethylene glycol 20-442 parts, benzoic acid 34-43 parts, phthalic anhydride 102-105 parts, maleic anhydride 240-246 parts, antioxidant 0.4-0.5 parts, first polymerization inhibitor 0.01-0.05 parts, second polymerization inhibitor 0.05-0.08 parts, third polymerization inhibitor 0.01-0.03 parts, defoamer 0.97-1.05 parts, surfactant 0.95-1.05 parts, stabilizer The mixture comprises 0.01-0.03 parts of a fixative, 230-250 parts of a crosslinking agent, and 85-125 parts of a solvent; wherein the molar ratio of total alcohol to total acid is 1.03-1.13:1; the molar ratio of unsaturated acid to saturated acid is 2.5-2.517:1; the mass ratio of benzoic acid to surfactant is 34.64-44:1; and the surfactant is at least one selected from γ-methacryloyloxypropyltrimethoxysilane, polyethylene glycol 400, and Span 80. The weight ratio of the first, second, and third polymerization inhibitors is 1:1 to 8:0.2 to 2. The first polymerization inhibitor is added during the prepolymerization and heating stages and needs to exert its initial polymerization inhibition effect at medium to high temperatures. The second polymerization inhibitor further blocks the activity of residual free radicals in the early stage of cooling. The third polymerization inhibitor stabilizes the system in the low-temperature stage.

2. The light-transmitting resin according to claim 1, characterized in that: The first, second, and third polymerization inhibitors are at least one of methylhydroquinone, hydroquinone, and 4-tert-butylcatechol.

3. The light-transmitting resin according to claim 1, characterized in that, By weight, it also includes the following components: 30.8-31.2 parts of diethylene glycol, 27.8-28.2 parts of propylene glycol, and 12.8-13.2 parts of glycerol.

4. The light-transmitting resin according to claim 1, characterized in that: The ethylene glycol comprises 20-241 parts of crude ethylene glycol with a content of 60%-88% and 0-200 parts of distilled ethylene glycol with a content of 88%-95%.

5. A method for preparing a light-transmitting resin according to any one of claims 1 to 4, characterized in that: Includes the following steps: (1) Add ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, antioxidant and first polymerization inhibitor into the reaction vessel, heat up and prepolymerize for 0.5~2h; (2) After the prepolymerization reaction is completed, the temperature is raised to 200~204℃ and held until the acid value is 28.2~32.6mg / KOH and the cone-plate viscosity is 490.0~528.9mPa•s; the heating rate is 10~15℃ / h; (3) Cool down and add the second polymerization inhibitor, continue to cool down and add the third polymerization inhibitor, crosslinking agent, surfactant, stabilizer and defoamer and mix well; then cool down and add solvent and mix well; to obtain light-transmitting resin.

6. The method for preparing a light-transmitting resin according to claim 5, characterized in that: The specific operation of step (1) is to add ethylene glycol, maleic anhydride, phthalic anhydride, benzoic acid, antioxidant and first polymerization inhibitor into the reaction vessel, heat to 160~165℃ to react and release water, and then carry out a prepolymerization reaction for 0.5~2h.

7. The method for preparing a light-transmitting resin according to claim 5, characterized in that: The specific operation of step (3) is to cool down to 188~193℃ and add the second polymerization inhibitor, continue to cool down to 150~170℃ and add the third polymerization inhibitor, crosslinking agent, surfactant, stabilizer and defoamer and mix well; then cool down to 60~70℃ and add solvent and mix well; cool down to ≤50℃ to obtain light-transmitting resin.

8. The application of the light-transmitting resin according to any one of claims 1 to 4 or the light-transmitting resin prepared by the method according to any one of claims 5 to 7, characterized in that: Applications in the field of skylight tiles.

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