Sulfonated modified polyether, preparation method and application of sulfonated modified polyether as internal release agent in thermosetting resin demolding

Abstract

The invention discloses sulfonated modified polyether, a preparation method and application of the sulfonated modified polyether as an internal release agent in thermosetting resin demolding, the sulfonated modified polyether can be used as the internal release agent in thermosetting resin demolding, the preparation is simple, the compatibility with thermosetting resin is good, the demolding efficiency of the thermosetting resin can be improved, and the service life of the thermosetting resin is prolonged. And the reaction speed of the thermosetting resin can be delayed. The sulfonated modified polyether disclosed by the invention has a structure as shown in the following formula I: in a # imgabs0 # formula, R1, R2... Rx are respectively one or more of H,-SO3Na or-SO3NH4 substituent groups, and R1, R2... Rx cannot be all H; when R1, R2... Rx are all H, the formula I is a structural general formula for preparing a sulfonated modified polyether raw material, namely polyether polyol, and R represents an initiator and is one or more of ethylene glycol, propylene glycol, glycerol or sorbitol; x is any integer of 2-4, and represents that the functionality of the polyether polyol is 2-4; n1 + n2... nx + m1 + m2... mx are integers from 20 to 2000 and represent repetitive units of the polyether polyol.

Description

Technical Field

[0001] The present invention relates to a polyether, a preparation method and an application thereof, and more particularly to a sulfonated modified polyether, a preparation method and an application thereof as an internal release agent in thermosetting resin demoulding. Background Art

[0002] As my country's urbanization and industrialization gradually accelerate, the demand for composite materials in the fields of construction, transportation, new energy, etc. is increasing. Thermosetting resin composite materials are gradually replacing metal materials such as aluminum profiles and steel components with the advantages of fast molding, simple processing, excellent corrosion resistance and wear resistance, light weight and good mechanical properties. Thermosetting resin composite materials are widely used in door and window profiles, air conditioning shutters, air conditioning brackets and various right-angle, I-shaped, hollow special-shaped profiles. The mainstream thermosetting resin composite molding process is divided into injection molding, compression molding and pultrusion molding. In conventional thermosetting resin composite materials, about 80% of glass fiber is contained to enhance its mechanical properties. Thermosetting resin resin is added to the mold by injection molding process, the glass fiber is fully immersed, and the thermosetting resin product is demolded after curing. The above injection molding process involves the demolding problem of thermosetting resin products. The use of a demolding agent can effectively reduce the bonding between the thermosetting resin product and the mold, and improve the yield rate and production efficiency. Therefore, the selection of a demolding agent has many requirements for economic effect, product quality and demolding effect. A poor release agent will cause cracks and wrinkles on the product surface, affecting the quality and service life of the product.

[0003] The mainstream thermosetting resin release agent is compounded with natural wax, higher fatty acid, fatty acid soap, mineral oil, silicone, polyvinyl alcohol and cellulose acetate. When used, it is applied to the inner surface of the mold to form a micron-level thermally stable protective film to isolate the thermosetting resin material and the mold to achieve the effect of anti-sticking. This type of release agent needs to be sprayed before the material is produced. The demoulding effect can only be maintained a few times after one spraying, and it is easy to cause pollution to the production mold. In addition, whether the spraying of the release agent is uniform will seriously affect the demoulding effect. Unevenly dispersed release agents may even cause fine defects on the surface of the product. In addition, when thermosetting resins are used to prepare glass fiber toughened composite materials, injection molding technology is used, which requires the thermosetting resin to be able to cure quickly at the curing temperature, and when the resin just enters the mold, a certain flow time is required to completely infiltrate the glass fiber. Generally, adding a reaction delay agent (such as lactic acid, acetylacetone, etc.) not exceeding 0.1% by mass to the thermosetting resin can significantly delay the reaction speed of the resin in the mold and improve the infiltration efficiency of the resin on the glass fiber.

[0004] In the prior art, the Chinese patent with publication number CN112680208A discloses a kind of oleyl alcohol polyoxyethylene ether using a membrane sulfonator, using SO3 as a sulfonating agent, neutralized with an alkaline solution, and obtaining oleyl alcohol polyoxyethylene ether sulfonate, which is used as a salt-resistant surfactant and applied to the field of oil production. The Chinese patent with publication number CN114276281A discloses a kind of cardanol polyoxyethylene ether using aminosulfonic acid as a sulfonating agent, adding a reducing agent as a color stabilizer, and obtaining light-colored cardanol polyoxyethylene ether ammonium sulfate, which is applied to daily chemical cleaning surfactants. The Chinese patent with publication number CN101279937A discloses a kind of nonylphenol sulfonic acid polyoxyethylene ether using sodium sulfite as a sulfonating agent, and preparing nonylphenol sulfonic acid polyoxyethylene ether sodium sulfonate, which is applied to high temperature and high salt oil displacement in oil production. In the prior art, the sulfonation modification of macromolecular polyols is generally used as a surfactant, which is applied to the fields of oil production oil displacement, daily chemical cleaning, and does not involve the application as a release agent. Summary of the invention

[0005] The purpose of the present invention is to solve the problems that the existing release agent needs to be sprayed in advance when used, the dispersion effect is unstable, and the mold is easily contaminated. A sulfonated modified polyether is provided. The sulfonated modified polyether can be used as an internal release agent in thermosetting resin demolding. The sulfonated modified polyether is simple to prepare and has good compatibility with thermosetting resin. It can not only improve the demolding efficiency of thermosetting resin, but also delay the reaction speed of thermosetting resin.

[0006] The invention also provides a method for preparing the sulfonated modified polyether, which is simple and easy to prepare under mild conditions.

[0007] The present invention is achieved through the following technical solutions:

[0008] The sulfonated modified polyether of the present invention has a structure as described in the following formula I:

[0009]

[0010] In the formula, R1, R2...R x are one or more of H, -SO3Na or -SO3NH4, and R1, R2...R x Cannot all be H; when R1, R2...R x When all are H, Formula I is the general structural formula for preparing the sulfonated modified polyether raw material, i.e., polyether polyol, wherein R represents the starting material, which is one or more of ethylene glycol, propylene glycol, glycerol or sorbitol; x is any integer from 2 to 4, representing that the functionality of the polyether polyol is 2 to 4; n1+n2...n x +m1+m2...m x An integer of 20-2000 is taken to represent the repeating unit of the polyether polyol.

[0011] The sulfonated modified polyether of the present invention has a further technical solution that the polyether polyol is synthesized by using ethylene glycol as a starting material and ethylene oxide as a polymerization monomer, and a bimetallic catalyst is used in the synthesis, m1+m2...m x =50-80, the molecular chain of the polyether polyol is highly regular, the molecular weight is 500-10000, and the functionality is 2-4. A further technical solution is that the molecular weight of the polyether polyol is preferably 2000-6000, and the functionality is preferably 2.

[0012] The sulfonated modified polyether of the present invention can also be further technically comprised of the R1, R2...R x It is -SO3NH4 group.

[0013] The preparation method of the sulfonated modified polyether of the present invention mainly comprises the following steps: adding a sulfonating agent to a polyether polyol under the action of a catalyst to carry out a sulfonation reaction; after the reaction is complete, removing the generated solid precipitate by vacuum filtration to obtain a sulfonated modified polyether.

[0014] The preparation method of the sulfonated modified polyether of the present invention has a further technical solution that the catalyst is one of N,N-dimethylformamide, p-toluenesulfonic acid or urea or a combination thereof, and the addition amount is 0.2-0.5% of the mass of the polyether polyol raw material; the sulfonation reagent is one of chlorosulfonic acid, sulfur trioxide, sodium sulfite, aminosulfonic acid or a combination thereof, and the addition amount is 8-12% of the mass of the polyether polyol raw material; the sulfonation reaction temperature is 90-120°C, and the reaction time is 3-10h. A further technical solution is that the catalyst is preferably urea; the sulfonation reagent is preferably aminosulfonic acid; the sulfonation reaction temperature is preferably 110°C, and the reaction time is preferably 5h.

[0015] The sulfonated modified polyether of the present invention is used as an internal release agent in thermosetting resin demoulding.

[0016] The use of the sulfonated modified polyether as an internal mold release agent in thermosetting resin demoulding of the present invention has a further technical solution that the amount of the sulfonated modified polyether used as the internal mold release agent is 1.5-2.5% of the mass of the thermosetting resin.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The invention selects a specific polyether polyol raw material, uses an appropriate sulfonation reagent, and modifies the polyether polyol under the action of a catalyst to prepare a sulfonated modified polyether. The sulfonated modified polyether is used as an internal mold release agent, and the effect of the mold release agent meets expectations in various tests.

[0019] When the sulfonated modified polyether of the present invention is used as an internal mold release agent in thermosetting resin demoulding, it has a good demoulding effect, can delay the reaction speed of the thermosetting resin, and effectively prolong the flow time of the thermosetting resin. At the same time, the modified polyether of the present invention is used as an internal mold release agent for thermosetting resin to effectively improve the demoulding efficiency of thermosetting resin products; compared with the use of an external mold release agent, the production process is simplified and the quality of the mold and the thermosetting resin product will not be affected. DETAILED DESCRIPTION

[0020] The present invention is described below by means of specific examples, but the present invention is not limited to these examples.

[0021] In the following embodiments, comparative examples and application examples, the polyether polyol model is LSE-2038, which is synthesized with ethylene glycol as the initiator and propylene oxide as the polymerization monomer, with a molecular weight of 3000, produced by Shandong Longhua New Materials Co., Ltd.; the polyether polyol model is LMN-3050D, which is synthesized with propylene oxide as the initiator and propylene oxide as the polymerization monomer, with a molecular weight of 5000, produced by Shandong Longhua New Materials Co., Ltd.; the polyether polyol model is LEP-330N, which is synthesized with propylene oxide as the initiator and propylene oxide as the polymerization monomer, ethylene oxide capped, with a molecular weight of 3000, produced by Shandong Longhua New Materials Co., Ltd. The company produces; the polyether polyol model is LSE-6010, which is synthesized with sorbitol as the initiator and propylene oxide as the polymerization monomer, with a molecular weight of 10,000, and is produced by Shandong Longhua New Materials Co., Ltd.; the polyether polyol model is code-named polyol-A1, which is synthesized with ethylene glycol as the initiator and ethylene oxide as the polymerization monomer, with a molecular weight of 5,000, and is produced by Covestro Polymer (China) Co., Ltd.; the polyether polyol model is polyol-A2, which is synthesized with ethylene glycol as the initiator and propylene oxide as the polymerization monomer, and is terminated with ethylene oxide, with a molecular weight of 4,000, and is produced by Covestro Polymer (China) Co., Ltd.

[0022] Example 1

[0023] 500g polyether polyol (LSE-2038), 0.6g N,N-dimethylformamide and 0.6g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 31.1g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 1 (referred to as release agent 1) was obtained, and its structural formula is as follows:

[0024]

[0025] Where n1 and n2 are integers between 24 and 28.

[0026] Example 2

[0027] 500g polyether polyol (LMN-3050D), 0.6g N,N-dimethylformamide and 0.6g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 29.4g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 2 (referred to as release agent 2) was obtained, and its structural formula is as follows:

[0028]

[0029] Among them, n1, n2, and n3 are integers between 40 and 45.

[0030] Example 3

[0031] 500g polyether polyol (LEP-330N), 0.6g N,N-dimethylformamide and 0.6g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 29.3g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 3 (referred to as release agent 3) was obtained, and its structural formula is as follows:

[0032]

[0033] Among them, n1, n2, and n3 are integers between 15 and 20, and m1, m2, and m3 are integers between 2 and 5.

[0034] Example 4

[0035] 500g of polyether polyol (LEP-6010), 9.3g of N,N-dimethylformamide and 9.3g of urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 466.8g of aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 4 (referred to as release agent 4) was obtained, and its structural formula is as follows:

[0036]

[0037] Among them, n1, n2, n3, n4, n5, and n6 are integers between 0 and 60, and the average functionality of polyether polyol LEP-6010 is 4.5, which means that n1, n2, n3, n4, n5, and n6 have a value of 0, which means that the hydroxyl group of the starting material sorbitol is not completely replaced.

[0038] Example 5

[0039] 500g polyether polyol (polyol-A1), 0.5g N,N-dimethylformamide and 0.5g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 26g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 5 (referred to as release agent 5) was obtained, and its structural formula is as follows:

[0040]

[0041] Among them, n1 and n2 are integers between 25 and 30, and m1 and m2 are integers between 5 and 10.

[0042] Example 6

[0043] 500g polyether polyol (polyol-A2), 0.5g N,N-dimethylformamide and 0.5g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 24g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After filtering the product to separate the solid residue, a sulfonated modified polyether product 6 (referred to as release agent 6) was obtained, and its structural formula is as follows:

[0044]

[0045] Where n1 and n2 are integers between 75 and 80.

[0046] Example 7

[0047] 500g polyether polyol (polyol-A2) and 1g N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 24g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0048] Example 8

[0049] 500g polyether polyol (polyol-A2) and 1g p-toluenesulfonic acid were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 24g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0050] Example 9

[0051] 500g polyether polyol (polyol-A2) and 1g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 24g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the residual solid content and the acid value of the sulfonated modified polyether were detected to calculate the degree of sulfonation (see Table 4 for details).

[0052] Example 10

[0053] 500g polyether polyol (polyol-A2) and 1g sodium hydroxide were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 90°C, and stirred for 1h. 28.8g chlorosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the residual solid content and the acid value of the sulfonated modified polyether were detected, and the sulfonation degree was calculated (see Table 4 for details). Its structural formula is as follows:

[0054]

[0055] Where n1 and n2 are integers between 75 and 80.

[0056] Embodiment 11

[0057] 500g polyether polyol (polyol-A2), 1g sodium hydroxide and 10g ultrapure water were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 90°C, and stirred for 1h. 28.8g chlorosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0058] Example 12

[0059] 500g of polyether polyol (polyol-A2) and 1g of urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 12g of aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the residual solid content and the acid value of the sulfonated modified polyether were detected, and the sulfonation degree was calculated (see Table 4 for details), and the sulfonated modified polyether product 7 (referred to as release agent 7) was obtained.

[0060] Embodiment 13

[0061] 500g polyether polyol (polyol-A2) and 1g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 100°C, and stirred for 1h. 12g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0062] Embodiment 14

[0063] 500g polyether polyol (polyol-A2) and 1g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 120°C, and stirred for 1h. 12g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 5h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0064] Embodiment 15

[0065] 500g polyether polyol (polyol-A2) and 1g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 12g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 3h until the reaction was complete. After the product was filtered to separate the solid residue, the degree of sulfonation was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0066] Example 16

[0067] 500g polyether polyol (polyol-A2) and 1g urea were added to a three-necked flask equipped with a stirrer and a thermometer, the system temperature was controlled at 110°C, and stirred for 1h. 12g aminosulfonic acid was added, the reaction temperature was maintained, and the reaction was continued for 10h until the reaction was complete. After the product was filtered to separate the solid residue, the sulfonation degree was calculated by detecting the residual solid content and the acid value of the sulfonated modified polyether (see Table 4 for details).

[0068] Application Examples

[0069] In order to evaluate the demolding effect of the prepared thermosetting resin internal release agent (release agent 1 to release agent 7), a homemade thermosetting resin formula was used. Resin component A is polymethylene polyphenyl polyisocyanate (PMDI). Resin component B is a combined polyether, in which polyether polyol 1 is a polyether polyol with a molecular weight of 6000 and a functionality of 4; polyether polyol 2 is a polyether polyol with a molecular weight of 500-800 and a functionality of 3; polyether polyol 3 is a polyether polyol with a molecular weight of 200-500 and a functionality of 2; the small molecule chain extender is glycerol; the organic metal catalyst used as the catalyst is an organic bismuth catalyst or an organic tin catalyst. The amount of sulfonated modified polyether used as an internal release agent in the combined polyether accounts for about 2%. The proportion of each component in the specific formula is shown in the following table:

[0070] Table 1: Combination formula of heat-curing thermosetting resin B for effect evaluation (numbers represent the proportion of each component)

[0071]

[0072] The above release agent is added to the combined polyether (the formula is shown in Table 1) to prepare different resin B components, and the A component is added and mixed to obtain a thermosetting resin. The resin sample is taken for curing test on a thermal gelator, and the thermal gel time of the resin sample is recorded. After the sample is cured, it is manually demolded and the demolding difficulty is evaluated. Take 100g of the newly prepared thermosetting resin for dynamic gel time test, and record the gel time of the resin at 35°C (see Table 2 for details).

[0073] Comparative Example 1

[0074] The unsulfonated modified polyether polyol (polyol-A2) was added as a release agent to the combined polyether (see Table 1 for the formula) to prepare the resin component B, and the A component was added and mixed to obtain a thermosetting resin. The resin sample was taken and cured on a thermal gelator, and the thermal gel time of the resin sample was recorded. After the sample was cured, it was manually demolded and the demolding difficulty was evaluated. An appropriate amount of resin was used for the dynamic gel time test, and the gel time of the resin at 35°C was recorded (see Table 2 for details).

[0075] Comparative Example 2

[0076] The combined polyether (formula as shown in Table 1) without any release agent was mixed with component A as resin component B to obtain a thermosetting resin. The resin sample was cured on a thermogelator and the thermogel time of the resin sample was recorded. After the sample was cured, it was manually demolded and the demolding difficulty was evaluated. An appropriate amount of resin was used for the dynamic gel time test and the gel time of the resin at 35°C was recorded (see Table 2 for details).

[0077] In order to evaluate the usage of the prepared thermosetting resin internal release agent and its effect on the demoulding effect and the reaction delay effect, based on the formula in Table 1, the mass proportion of the release agent in the thermosetting resin B combination was adjusted to a range of 1-4%. Release agent 6 (preparation details see Example 6) was used as a test sample, and the specific demoulding effect and reaction delay effect are shown in Table 3.

[0078] Table 2: Evaluation of demoulding effect and reaction delay effect of sulfonated polyether

[0079]

[0080] Note: The demoulding effect is evaluated by the degree of difficulty of demoulding on the heating plate (1-10), and the higher the score, the better the demoulding effect; the above results are the average of the data obtained from three parallel tests.

[0081] Table 3: Effect of different addition amounts of release agent 6 on demoulding effect and reaction delay effect

[0082]

[0083] Note: The demoulding effect is evaluated by the degree of difficulty of demoulding on the heating plate (1-10), and the higher the score, the better the demoulding effect; the above results are the average of the data obtained from three parallel tests.

[0084] Table 4: Sulfonation degree of polyether polyols under different reaction conditions

[0085] Example Sulfonation reagent catalyst Reaction temperature Reaction time Sulfonation degree 7 Sulfamic acid DMF 110 5h 47.2％ 8 Sulfamic acid p-Toluenesulfonic acid 110 5h 35.5％ 9 Sulfamic acid Urea 110 5h 82.0％ 10 Chlorosulfonic acid Sodium hydroxide 90 5h 21.3％ 11 Chlorosulfonic acid Sodium hydroxide 90 5h 40.5％ 12 Sulfamic acid Urea 110 5h 37.7％ 13 Sulfamic acid Urea 100 5h 74.5％ 14 Sulfamic acid Urea 120 5h 81.5％ 15 Sulfamic acid Urea 110 3h 65.3％ 16 Sulfamic acid Urea 110 10h 83.1％

[0086] The demoulding effects of Examples 1 to 6 and Example 12 show that the polyether polyol used for sulfonation modification is preferably a polyether polyol with ethylene glycol as the starting material, ethylene oxide as the polymerization monomer, and a molecular weight of 2000-6000. The delayed effect of Examples 1 to 6 and Example 12 on the reaction of thermosetting resins shows that the examples with good demoulding effects can also delay the reaction rate of thermosetting resins. It can be seen from the comparative examples that the sulfonated modified polyether prepared in the examples of the present invention is used as an internal demoulding agent for thermosetting thermosetting resins and has good demoulding properties. After being cured on a thermogelator, the thermosetting thermosetting resin without adding an internal demoulding agent will adhere to the heating plate and is difficult to demould completely. After being cured on a thermogelator, the thermosetting thermosetting resin to which the unsulfonated modified polyether polyol is added has a certain demoulding effect. The thermosetting resin with an internal demoulding agent can be demoulded easily. The dynamic gel time test was carried out on the thermosetting resin samples added with the example samples and the blank (Comparative Example 2). The experimental results show that the internal release agent prepared by the present invention can delay the reaction speed of the thermosetting resin and effectively prolong the operable time of the thermosetting resin. The data in Table 3 show that when the amount of sulfonated modified polyether is 1.5% of the mass of the thermosetting resin, the demoulding effect of the thermosetting resin is better; when the amount is greater than 1.5%, the operable time of the thermosetting resin is significantly improved, but when the amount is greater than 3%, the heat curing time and gelling time of the thermosetting resin are significantly prolonged, which does not meet the production requirements. In general, the applicable range of the amount of sulfonated modified polyether is 1.5-2.5% of the mass of the thermosetting resin. As an auxiliary agent, the sulfonated modified polyether is added to the thermosetting resin B component in an appropriate amount (1.5-2.5%), which will not affect its normal heat curing and can prolong the operable time of the resin. The above results confirm that the modified polyether prepared by the present invention has good performance as an additive auxiliary agent for thermosetting resin products. In particular, by comparing the sulfonation degrees of Examples 7 to 16, the optimal conditions for the sulfonation modification process of polyether polyols are: using urea as a catalyst, aminosulfonic acid as a sulfonation agent, a reaction temperature of 110° C., and a reaction time of 5 h.

Claims

1. A sulfonated modified polyether, characterized in that: Having the structure as described in the following formula I: In the formula, R1, R2...R x are one or more of H, -SO3Na or -SO3NH4, and R1, R2...R x Cannot all be H; when R1, R2...R x When all are H, Formula I is the general structural formula for preparing the sulfonated modified polyether raw material, i.e., polyether polyol, wherein R represents the starting material, which is one or more of ethylene glycol, propylene glycol, glycerol or sorbitol; x is any integer from 2 to 4, representing that the functionality of the polyether polyol is 2 to 4; n1+n2...n x +m1+m2...m x An integer of 20-2000 is taken to represent the repeating unit of the polyether polyol.

2. The sulfonated modified polyether according to claim 1, characterized in that: The polyether polyol is synthesized by using ethylene glycol as the starting material and ethylene oxide as the polymerization monomer. A bimetallic catalyst is used in the synthesis. m1+m2...m x =50-80, the molecular chain of polyether polyol is highly regular, the molecular weight is 500-10000, and the functionality is 2-4.

3. The sulfonated modified polyether according to claim 2, characterized in that: The molecular weight of the polyether polyol is 2000-6000 and the functionality is 2.

4. The sulfonated modified polyether according to claim 1, characterized in that: The R1, R2...R x It is -SO3NH4 group.

5. A method for preparing a sulfonated modified polyether as claimed in any one of claims 1 to 4, characterized in that: The main steps include: The polyether polyol is added with a sulfonating agent under the action of a catalyst to carry out a sulfonation reaction; after the reaction is completed, the solid precipitate is removed by vacuum filtration to obtain a sulfonated modified polyether.

6. The method for preparing the sulfonated modified polyether according to claim 5, characterized in that: The catalyst is one of N,N-dimethylformamide, p-toluenesulfonic acid or urea or a combination thereof, and the added amount is 0.2-0.5% of the mass of the polyether polyol raw material; the sulfonation reagent is one of chlorosulfonic acid, sulfur trioxide, sodium sulfite, aminosulfonic acid or a combination thereof, and the added amount is 8-12% of the mass of the polyether polyol raw material; the sulfonation reaction temperature is 90-120°C, and the reaction time is 3-10h.

7. The method for preparing the sulfonated modified polyether according to claim 6, characterized in that: The catalyst is urea; the sulfonation reagent is aminosulfonic acid; the sulfonation reaction temperature is 110° C., and the reaction time is 5 hours.

8. Use of the sulfonated modified polyether as claimed in any one of claims 1 to 4 as an internal release agent in thermosetting resin demoulding.

9. The use of the sulfonated modified polyether according to claim 8 as an internal release agent in thermosetting resin demoulding, characterized in that: When the sulfonated modified polyether is used as an internal mold release agent, its usage is 1.5-2.5% of the mass of the thermosetting resin.

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