CN116178635A - Method for preparing mould pressing resin - Google Patents

Method for preparing mould pressing resin Download PDF

Info

Publication number
CN116178635A
CN116178635A CN202211609393.7A CN202211609393A CN116178635A CN 116178635 A CN116178635 A CN 116178635A CN 202211609393 A CN202211609393 A CN 202211609393A CN 116178635 A CN116178635 A CN 116178635A
Authority
CN
China
Prior art keywords
dihydric alcohol
producing
resin
molded resin
resin according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211609393.7A
Other languages
Chinese (zh)
Inventor
王向东
陈继荣
杨晓峰
万永丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Rixin Resin Co ltd
Original Assignee
Changzhou Rixin Resin Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou Rixin Resin Co ltd filed Critical Changzhou Rixin Resin Co ltd
Priority to CN202211609393.7A priority Critical patent/CN116178635A/en
Publication of CN116178635A publication Critical patent/CN116178635A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to the technical field of polyester resin, in particular to a preparation method of mould pressing resin, which comprises the following steps: s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, partial dibasic alcohol and auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g; s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 11-12p/140 ℃; s3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the molded resin; the dihydric alcohol adopts dipropylene glycol, neopentyl glycol and pentaerythritol, and the dipropylene glycol can improve the flexibility and corrosion resistance of the resin; neopentyl glycol improves the corrosion resistance, in particular the alkali resistance and the hydrolytic stability of the resin, and pentaerythritol improves the flexibility and the corrosion resistance of the resin.

Description

Method for preparing mould pressing resin
Technical Field
The invention relates to the technical field of polyester resin, in particular to a preparation method of mould pressing resin.
Background
The unsaturated polyester resin is a linear polymer compound having an ester bond and an unsaturated double bond, which is obtained by polycondensation of an unsaturated dibasic acid diol or a saturated dibasic acid unsaturated diol. Under the action of the accelerator and the curing agent, the catalyst can be subjected to chemical crosslinking reaction with the diluent styrene to form a solid with a three-dimensional network structure, and the product is often used in the SMC/BMC field due to small volatilization of the solvent in the use process and environmental protection.
Disclosure of Invention
The purpose of the invention is that: a method for producing a molding resin is provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for producing a molded resin, the method comprising the steps of:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, partial dibasic alcohol and auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 11-12p/140 ℃;
s3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the molding resin.
Further, the first dibasic acid anhydride is tetrahydrophthalic anhydride, and the second dibasic acid anhydride is maleic anhydride.
Further, the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
Further, the dihydric alcohol one and the dihydric alcohol two are selected from one of propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol and pentaerythritol.
Further, the dihydric alcohol I is dipropylene glycol, the dihydric alcohol II is neopentyl glycol and pentaerythritol, and the molar ratio is 1:0.45:0.05.
Further, in the step S1, the outlet temperature of the reflux condenser is controlled to be below 102 ℃ so as to avoid volatilization loss of the dihydric alcohol.
Furthermore, the auxiliary agent in the step S1 is trimellitic anhydride.
Further, the heating reaction in the step S1 is to heat up to 235-245 ℃ within 3 hours and keep the temperature for reaction, and the heating reaction in the step S2 is to heat up to 180-185 ℃ and then gradually heat up to 215-220 ℃ and keep the temperature for reaction.
Further, in the step S3, the mass ratio of the unsaturated polyester to the styrene is 7:3.
Further, the polymerization inhibitor in the step S3 is selected from one of hydroquinone and copper naphthenate.
The technical scheme of the invention has the beneficial effects that:
the dihydric alcohol adopts dipropylene glycol, neopentyl glycol and pentaerythritol, and the dipropylene glycol can improve the flexibility and corrosion resistance of the resin; neopentyl glycol improves the corrosion resistance, in particular the alkali resistance and the hydrolytic stability of the resin, and pentaerythritol improves the flexibility and the corrosion resistance of the resin.
Styrene is a low viscosity liquid, has good compatibility with resins and various auxiliary components, and can form a copolymer with uniform components when being copolymerized with unsaturated polyester resins.
According to the invention, part of the dihydric alcohol is added first, and the outlet temperature of the reflux condenser is controlled, so that excessive volatilization of the dihydric alcohol can be avoided, the addition amount of the dihydric alcohol is reduced, and the production efficiency of the product is improved.
Detailed Description
The method for producing the molding resin of the present invention will be further described with reference to the embodiments of the present specification.
The method for producing the molded resin in this embodiment includes the steps of:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, partial dibasic alcohol and auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 11-12p/140 ℃;
s3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the molding resin.
Wherein, the dibasic acid anhydride I is tetrahydrophthalic anhydride, the dibasic acid anhydride II is maleic anhydride, and the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
Wherein the dihydric alcohol I and the dihydric alcohol II are selected from one of propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol and pentaerythritol, the dihydric alcohol I is dipropylene glycol, the dihydric alcohol II is neopentyl glycol and pentaerythritol, and the mol ratio is 1:0.45:0.05.
The outlet temperature of a reflux condenser in the step S1 is controlled below 102 ℃ so as to avoid volatilization loss of dihydric alcohol, the auxiliary agent in the step S1 is trimellitic anhydride, the heating reaction in the step S1 is that the temperature is raised to 235-245 ℃ within 3h and the heat preservation reaction is carried out, the heating reaction in the step S2 is that the temperature is raised to 180-185 ℃ firstly, then the temperature is raised to 215-220 ℃ gradually and the heat preservation reaction is carried out, the mass ratio of unsaturated polyester to styrene in the step S3 is 7:3, and the polymerization inhibitor in the step S3 is one of hydroquinone and copper naphthenate.
The dihydric alcohol adopts dipropylene glycol, neopentyl glycol and pentaerythritol, and the dipropylene glycol can improve the flexibility and corrosion resistance of the resin; neopentyl glycol improves the corrosion resistance, in particular the alkali resistance and the hydrolytic stability of the resin, and pentaerythritol improves the flexibility and the corrosion resistance of the resin. Styrene is a low viscosity liquid, has good compatibility with resins and various auxiliary components, and can form a copolymer with uniform components when being copolymerized with unsaturated polyester resins.
Example 1
The method for producing the molded resin in this embodiment includes the steps of:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, 1/3 amount of dibasic alcohol and an auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g; the outlet temperature of the reflux condenser is controlled below 102 ℃ to avoid volatilization loss of dihydric alcohol, the auxiliary agent is trimellitic anhydride, and the heating reaction in the step S1 is to heat up to 235+/-2 ℃ within 3 hours and keep the temperature for reaction;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 11p/140 ℃; heating reaction means that the temperature is firstly increased to 180+/-1 ℃, then the temperature is gradually increased to 215+/-1 ℃ and the temperature is kept for reaction;
and S3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the die-pressing resin, wherein the mass ratio of unsaturated polyester to styrene in the step S3 is 7:3, and the polymerization inhibitor in the step S3 is one of hydroquinone and copper naphthenate.
Wherein, the dibasic acid anhydride I is tetrahydrophthalic anhydride, the dibasic acid anhydride II is maleic anhydride, and the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
Wherein the first dihydric alcohol is diethylene glycol, the second dihydric alcohol is neopentyl glycol, and the molar ratio of the diethylene glycol to the neopentyl glycol is 1:1.
Example 2
The method for producing the molded resin in this embodiment includes the steps of:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, 1/3 amount of dibasic alcohol and an auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g; the outlet temperature of the reflux condenser is controlled below 102 ℃ to avoid volatilization loss of dihydric alcohol, the auxiliary agent is trimellitic anhydride, and the heating reaction in the step S1 is that the temperature is raised to 240+/-2 ℃ within 3 hours and the heat is preserved for reaction;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 12p/140 ℃; heating reaction means that the temperature is firstly increased to 185+/-2 ℃, then the temperature is gradually increased to 218+/-2 ℃ and the temperature is kept for reaction;
and S3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the die-pressing resin, wherein the mass ratio of unsaturated polyester to styrene in the step S3 is 7:3, and the polymerization inhibitor in the step S3 is one of hydroquinone and copper naphthenate.
Wherein, the dibasic acid anhydride I is tetrahydrophthalic anhydride, the dibasic acid anhydride II is maleic anhydride, and the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
Wherein the dihydric alcohol I is dipropylene glycol, the dihydric alcohol II is neopentyl glycol and pentaerythritol, and the molar ratio is 1:0.45:0.05.
Example 3
The method for producing the molded resin in this embodiment includes the steps of:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, 1/3 amount of dibasic alcohol and an auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g; the outlet temperature of the reflux condenser is controlled below 102 ℃ to avoid volatilization loss of dihydric alcohol, the auxiliary agent is trimellitic anhydride, and the heating reaction in the step S1 is to heat up to 245+/-2 ℃ within 3 hours and keep the temperature for reaction;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 12p/140 ℃; heating reaction means that the temperature is firstly increased to 185+/-2 ℃, then gradually increased to 220+/-2 ℃ and the temperature is kept for reaction;
and S3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the die-pressing resin, wherein the mass ratio of unsaturated polyester to styrene in the step S3 is 7:3, and the polymerization inhibitor in the step S3 is one of hydroquinone and copper naphthenate.
Wherein, the dibasic acid anhydride I is tetrahydrophthalic anhydride, the dibasic acid anhydride II is maleic anhydride, and the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
Wherein the dihydric alcohol I is dipropylene glycol, the dihydric alcohol II is neopentyl glycol and pentaerythritol, and the molar ratio is 1:0.45:0.05.
100g of the molding resin prepared in examples 1 to 3 was uniformly mixed with 0.1g of cobalt naphthenate and 1g of methyl ethyl ketone peroxide, cured at 80℃for 2 hours, cured at 100℃for 4 hours after the gel was solid, left at normal temperature for 24 hours, and then molded into a resin casting according to CB/T2567 and tested. The specific test results are shown in Table 1.
TABLE 1
Figure SMS_1
Furthermore, it should be understood that while the present description describes embodiments, not every embodiment is presented by way of example only, and that this description is provided for clarity only, and that the present disclosure is not limited to the embodiments described in the figures, as such, and that the embodiments described in the examples may be combined in any suitable manner to form other embodiments that will be apparent to those of skill in the art.

Claims (10)

1. The preparation method of the mould pressing resin is characterized in that: the preparation method comprises the following steps:
s1, introducing carbon dioxide into a reaction kettle, discharging air in the reaction kettle, adding dibasic acid anhydride, partial dibasic alcohol and auxiliary agent, and carrying out heating reflux reaction under the protection of nitrogen until the acid value is lower than 20+/-2 mgKOH/g;
s2, the temperature is reduced to be lower than 160 ℃, dibasic acid anhydride II, residual dihydric alcohol I and dihydric alcohol II are added, and heating reaction is carried out until the acid value is 28mgKOH/g and the viscosity is 11-12p/140 ℃;
s3, cooling to 175 ℃, adding a polymerization inhibitor, diluting with styrene, cooling and filtering to obtain the molding resin.
2. The method for producing a molded resin according to claim 1, wherein: the first dibasic acid anhydride is tetrahydrophthalic anhydride, and the second dibasic acid anhydride is maleic anhydride.
3. The method for producing a molded resin according to claim 2, wherein: the molar ratio of tetrahydrophthalic anhydride to maleic anhydride is 1:9.
4. The method for producing a molded resin according to claim 1, wherein: the dihydric alcohol I and the dihydric alcohol II are selected from one of propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol and pentaerythritol.
5. The method for producing a molded resin according to claim 4, wherein: the dihydric alcohol I is dipropylene glycol, the dihydric alcohol II is neopentyl glycol and pentaerythritol, and the molar ratio is 1:0.45:0.05.
6. The method for producing a molded resin according to claim 1, wherein: in the step S1, the outlet temperature of the reflux condenser is controlled below 102 ℃ so as to avoid volatilization loss of the dihydric alcohol.
7. The method for producing a molded resin according to claim 1, wherein: the auxiliary agent in the step S1 is trimellitic anhydride.
8. The method for producing a molded resin according to claim 1, wherein: the heating reaction in the step S1 is to heat to 235-245 ℃ within 3h and keep the temperature, and the heating reaction in the step S2 is to heat to 180-185 ℃ and then heat to 215-220 ℃ gradually and keep the temperature.
9. The method for producing a molded resin according to claim 1, wherein: the mass ratio of the unsaturated polyester to the styrene in the step S3 is 7:3.
10. The method for producing a molded resin according to claim 1, wherein: and the polymerization inhibitor in the step S3 is one of hydroquinone and copper naphthenate.
CN202211609393.7A 2022-12-14 2022-12-14 Method for preparing mould pressing resin Pending CN116178635A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211609393.7A CN116178635A (en) 2022-12-14 2022-12-14 Method for preparing mould pressing resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211609393.7A CN116178635A (en) 2022-12-14 2022-12-14 Method for preparing mould pressing resin

Publications (1)

Publication Number Publication Date
CN116178635A true CN116178635A (en) 2023-05-30

Family

ID=86437436

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211609393.7A Pending CN116178635A (en) 2022-12-14 2022-12-14 Method for preparing mould pressing resin

Country Status (1)

Country Link
CN (1) CN116178635A (en)

Similar Documents

Publication Publication Date Title
CN113061416A (en) High-strength high-toughness epoxy binder and preparation method thereof
CN107556464B (en) Synthetic method of unsaturated polyester resin for mould pressing
CN113583198B (en) Polyurethane acrylate composition and application thereof
US4338225A (en) High performance resin reaction products of carboxyl terminated 1,2-polybutadiene with epoxides and acid terminated difunctional aliphatic alcohols
WO2011092328A1 (en) Resin composition comprising isosorbide containing saturated polymer
US3931354A (en) Reaction products of carboxyl terminated 1,2-polybutadiene with epoxides and aromatic bis(maleimides)
CN116178635A (en) Method for preparing mould pressing resin
US4797464A (en) Diepoxide reacted with a half ester from a dicarboxyic acid anhydride and polyalkylene glycol
CN112029388B (en) Impregnating resin and preparation method thereof
US4929697A (en) Use of ester group containing polyols in a rim process
CN113583417A (en) Low-shrinkage unsaturated polyester resin for normal-temperature pouring and preparation method thereof
CN109880070B (en) Modified water-based polyester resin dispersoid for water-based baking paint and preparation method thereof
CN114276514B (en) Polyurethane-acrylic hybrid resin and application thereof
CN115073735A (en) Hyperbranched semi-aromatic polyester imide polymer and preparation method thereof
CN109054601B (en) Humidity-heat-resistant high-toughness modified unsaturated polyester solvent-free impregnating varnish and preparation method thereof
CN110885543B (en) Organic silicon modified unsaturated resin insulation impregnating resin and preparation method thereof
CN112552496A (en) Unsaturated polyester mold pressing resin, preparation method and application thereof
CN111499801A (en) Reactive type flame retardant capable of thickening, flame retardant vinyl SMC resin containing same and method for preparing same
US11248105B2 (en) Use of a branched polyester
JP3467884B2 (en) Oligomer excellent in curability, method for producing the oligomer, curable resin composition using the oligomer, and cured product obtained by curing the composition
CN110016127B (en) Synthetic method of water-based unsaturated polyester quartz resin
CN114736390B (en) Synthesis method of block polymerization epoxy modified unsaturated resin
CN114573798A (en) Hyperbranched polyester resin for coating and preparation method thereof
CN115746564B (en) Polysulfone composite material and preparation method and application thereof
CN114367257B (en) Polyester resin and preparation method and synthesis device thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination