CN102702252A - Phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] and synthesis method of phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] - Google Patents
Phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] and synthesis method of phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] Download PDFInfo
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- CN102702252A CN102702252A CN201210159929XA CN201210159929A CN102702252A CN 102702252 A CN102702252 A CN 102702252A CN 201210159929X A CN201210159929X A CN 201210159929XA CN 201210159929 A CN201210159929 A CN 201210159929A CN 102702252 A CN102702252 A CN 102702252A
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- dihydroxyphenyl propane
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Abstract
The invention discloses a phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] and a synthesis method of the phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate]. The phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] has large molecular weight, small mobility in plastic, small volatile organic compound ingredient and high hydrolytic stability. The product contains two flame retardant elements; the content of phosphorus is 7.5%, and the content of chlorine is 32.5%. The flame retardant elements can play a flame-retardation action in various plastic products after being combined with the other fire retardants.
Description
Technical field
The present invention relates to two [two (1, the 3-two chloropropyls) SULPHOSUCCINIC ACID ESTER] compounds of a kind of new type of phosphate based flame retardant dihydroxyphenyl propane, the preparation method of this compound is provided simultaneously.
Background technology
Urethane foam is one type of material that very easily catches fire; The fire retardant that is used for urethane foam can be divided into two types; One type is additive flame retardant, and another kind of is reactive flame retardant, and it is many that present additive flame retardant is used; Picture TCPP, chloro-phosphorus fire retardants such as TDCP are very general.The compound that these fire retardants are made up of two ignition-proof elements has synergy to flame retardant resistance; But because molecular weight is less than normal, their transport propertys in plastics are big, and the volatile organic matter composition is bigger; Stability to hydrolysis is lower, therefore suitably strengthens the flame retardant molecule amount and can overcome above shortcoming.
Summary of the invention
The present invention has synthesized a kind of new type of phosphate combustion inhibitor bisphenol A bis two [two (1,3-two chloropropyls) SULPHOSUCCINIC ACID ESTER], and its molecular weight is bigger, and transport property is little in plastics, and the volatile organic matter composition is smaller, and stability to hydrolysis is higher.The structural formula of dihydroxyphenyl propane two [two (1,3-two chloropropyls) SULPHOSUCCINIC ACID ESTER] (being called for short BCPP) is:
n=1-5。
Compound method is:
The first step adds dihydroxyphenyl propane in batches in POCl3, catalyzer magnesium dichloride, the mol ratio of POCl3 and dihydroxyphenyl propane is 2-8:1; Be optimized for 5-6:1, the consumption of catalyzer magnesium dichloride is the 0.1%-0.5% of reactant gross weight, heat temperature raising to 120 ℃-125 ℃; Be incubated 2.5-3.5 hour, during hydrogenchloride discharge, after reaction finishes; Underpressure distillation goes out excessive POCl3, obtains intermediate product;
Second step added the catalyzer aluminum chloride in intermediate product, catalyst levels is the 0.1%-0.5% of intermediate product weight; Between 65-70 ℃, drip epoxy chloropropane; The mol ratio of epoxy chloropropane and dihydroxyphenyl propane is 4.0-4.2:1, and the dropping time was controlled in 3-5 hour, is added dropwise to complete back system temperature of reaction and rises to 75 ℃-80 ℃; Be incubated 1-2 hour, get bullion;
In the 3rd step, adding volume ratio in the bullion is toluene and the hexanaphthene mixed solvent of 1:1, and the consumption of solvent is 2-4 a times of bullion weight, and underpressure distillation goes out solvent after pickling, alkali cleaning and washing, obtains product.
The first step is generated the chemical equation of midbody by POCl3 and dihydroxyphenyl propane reaction:
n=1-5
Midbody generates the chemical equation of BCPP again with epichlorohydrin reaction:
n=1-5
In the first step reaction, feed intake and under 95 ℃-100 ℃, carry out, in 1.5-2 hour, in batches the dihydroxyphenyl propane input is equipped with in the container of POCl3 and catalyzer, dihydroxyphenyl propane divides 5-15 to criticize input, is optimized for 8-10 and criticizes input.
In the 3rd step, bullion is to carry out a pickling with 2% hydrochloric acid soln earlier, carries out twice alkali cleaning with 2% sodium hydroxide again, washes twice again, and underpressure distillation goes out solvent, obtains product.
This product contains two ignition-proof elements, and wherein the content of phosphorus is 7.5%, and the content of chlorine is 32.5%.With it and other fire retardants carry out composite after, can in multiple plastics, play fire retardation.
Description of drawings
Fig. 1 is phosphorus-nuclear magnetic resonance spectrum of BCPP.
Fig. 2 is the fluid chromatograms do of BCPP.
Embodiment
Embodiment 1, in 2000 ml flasks, inserts whisking appliance, TM and reflux condensing tube, adds 923.6 gram (6 moles) POCl3s and 1.2 gram magnesium chloride catalyzer; Under constantly stirring, slowly heat temperature raising is to 95-100 ℃, and then in 1.5 hours, dividing feeds intake for 8 times adds 228 gram (1 mole) dihydroxyphenyl propanes; Feed intake accomplish after this system be warming up to 120-125 ℃; Be incubated 2.5-3.5 hour, in this reaction process, have hydrogen chloride gas to emit, absorb through resorber.Reaction finishes the back underpressure distillation and goes out excessive POCl3, obtains intermediate product 459.2 grams, and yield reaches 99.4%, and the POCl3 that distillation obtains can reuse.
Intermediate product is added 1.1 gram aluminum trichloride catalysts, between 65-70 ℃, drips epoxy chloropropane 367.1 grams (4 moles), is added dropwise to complete in 4 hours; 75-80 ℃ of insulation 1-2 hour, add toluene and hexanaphthene mixed solvent (volume ratio is 1:1), weight is 3 times of bullion weight; Carry out a pickling with 2% hydrochloric acid soln, carry out twice alkali cleaning with 2% sodium hydroxide again, again with twice of washing; Underpressure distillation goes out solvent, obtains product 759.7 grams, productive rate 91.4%.
The method of reference implementation example 1 changes the reference of each embodiment, as follows:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| POCl3 | 923.6g/6mol | 308g/2mol | 1232g/8mol | 770g/5mol |
| Magnesium chloride | 1.2g | 2.7g | 2.9g | 3.0g |
| Dihydroxyphenyl propane | 228g/1mol | 228g/1mol | 228g/1mol | 228g/1mol |
| Charging time | 1.5h | 2h | 2h | 1.5h |
| Number of times feeds intake | 8 |
5 | 15 | 10 |
| Intermediate product | 459.2g | 456.4g | 459.8g | 459.8g |
| The intermediate product yield | 99.4% | 98.8% | 99.5% | 99.5% |
| Aluminum chloride (0.1-0.5) | 1.1g(0.2%) | 1.1g(0.2) | 1.5g(0.3%) | 2.0g(0.4%) |
| Propylene oxide | 367.1g/4mol | 367.1g/4mol | 385.5g/4.2mol | 376.3g/4.1mol |
| Propylene oxide drips the time | 4h | 3h | 5h | 4h |
| The mixed solvent amount | 3 times of bullion weight | 2 times of bullion weight | 4 times of bullion weight | 4 times of bullion weight |
| Product | 759.7g | 751.2g | 768.1g | 762.8g |
| Productive rate | 91.4% | 90.3% | 92.3% | 91.7% |
Claims (6)
1. a phosphate flame retardant dihydroxyphenyl propane two [two (1,3-two chloropropyls) SULPHOSUCCINIC ACID ESTER] is characterized in that structural formula is:
n=1-5。
2. the compound method of phosphate flame retardant dihydroxyphenyl propane according to claim 1 two [two (1,3-two chloropropyls) SULPHOSUCCINIC ACID ESTER] is characterized in that:
The first step adds dihydroxyphenyl propane in batches in POCl3, catalyzer magnesium dichloride, the mol ratio of POCl3 and dihydroxyphenyl propane is 2-8:1; The consumption of catalyzer magnesium dichloride is the 0.1%-0.5% of reactant gross weight, and heat temperature raising to 120 ℃-125 ℃ is incubated 2.5-3.5 hour; Hydrogenchloride is discharged during this time; After reaction finished, underpressure distillation went out excessive POCl3, obtains intermediate product;
Second step added the catalyzer aluminum chloride in intermediate product, catalyst levels is the 0.1%-0.5% of intermediate product weight; Between 65-70 ℃, drip epoxy chloropropane; The mol ratio of epoxy chloropropane and dihydroxyphenyl propane is 4.0-4.2:1, and the dropping time was controlled in 3-5 hour, is added dropwise to complete back system temperature of reaction and rises to 75 ℃-80 ℃; Be incubated 1-2 hour, get bullion;
In the 3rd step, adding volume ratio in the bullion is toluene and the hexanaphthene mixed solvent of 1:1, and the consumption of solvent is 2-4 a times of bullion weight, and underpressure distillation goes out solvent after pickling, alkali cleaning and washing, obtains product.
3. compound method according to claim 2 is characterized in that the mol ratio of POCl3 and dihydroxyphenyl propane is 5-6:1 in the first step reaction.
4. compound method according to claim 2 is characterized in that feeding intake and under 95 ℃-100 ℃, carrying out in the first step reaction, in 1.5-2 hour, in batches the dihydroxyphenyl propane input is equipped with in the container of POCl3 and catalyzer, and dihydroxyphenyl propane divides 5-15 to criticize input.
5. compound method according to claim 4 is characterized in that dihydroxyphenyl propane divides 8-10 to criticize input.
6. compound method according to claim 2 is characterized in that the bullion in the 3rd step carries out a pickling with 2% hydrochloric acid soln, carries out twice alkali cleaning with 2% sodium hydroxide again, washes twice again, and underpressure distillation goes out solvent, obtains product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210159929XA CN102702252A (en) | 2012-05-22 | 2012-05-22 | Phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] and synthesis method of phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] |
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| CN201210159929XA CN102702252A (en) | 2012-05-22 | 2012-05-22 | Phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] and synthesis method of phosphate fire retardant bisphenol A bi[di(1,3-dichloropropyl) phosphate] |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219149A (en) * | 2018-02-22 | 2018-06-29 | 山东润科化工股份有限公司 | A kind of epoxy terminated hyper branched polyphosphate ester and preparation method thereof |
| CN109912646A (en) * | 2019-03-08 | 2019-06-21 | 南通江山农药化工股份有限公司 | The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A- |
| CN112142779A (en) * | 2020-10-13 | 2020-12-29 | 中国科学院宁波材料技术与工程研究所 | Rapid preparation method of bisphenol A bis (diaryl phosphate) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793152A (en) * | 2005-12-06 | 2006-06-28 | 河北工业大学 | Polycondenseng phosphate and its preparation process and application thereof |
| CN101200642A (en) * | 2006-12-11 | 2008-06-18 | 江苏雅克化工有限公司 | Bisphenol A(phenyl polyphosphoric acids easter) flame retardant and preparation thereof |
-
2012
- 2012-05-22 CN CN201210159929XA patent/CN102702252A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793152A (en) * | 2005-12-06 | 2006-06-28 | 河北工业大学 | Polycondenseng phosphate and its preparation process and application thereof |
| CN101200642A (en) * | 2006-12-11 | 2008-06-18 | 江苏雅克化工有限公司 | Bisphenol A(phenyl polyphosphoric acids easter) flame retardant and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| S. LEVCHIK ET AL.: ""New developments in flame retardancy of epoxy resins"", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219149A (en) * | 2018-02-22 | 2018-06-29 | 山东润科化工股份有限公司 | A kind of epoxy terminated hyper branched polyphosphate ester and preparation method thereof |
| CN108219149B (en) * | 2018-02-22 | 2020-12-01 | 山东润科化工股份有限公司 | Epoxy-terminated hyperbranched polyphosphate and preparation method thereof |
| CN109912646A (en) * | 2019-03-08 | 2019-06-21 | 南通江山农药化工股份有限公司 | The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A- |
| CN109912646B (en) * | 2019-03-08 | 2021-02-09 | 南通江山农药化工股份有限公司 | Preparation method of bisphenol A-bis (diphenyl phosphate) flame retardant |
| CN112142779A (en) * | 2020-10-13 | 2020-12-29 | 中国科学院宁波材料技术与工程研究所 | Rapid preparation method of bisphenol A bis (diaryl phosphate) |
| CN112142779B (en) * | 2020-10-13 | 2023-01-13 | 中国科学院宁波材料技术与工程研究所 | Rapid preparation method of bisphenol A bis (diaryl phosphate) |
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Application publication date: 20121003 |