CN1294158C - Production of structural fire-retardant plastic - Google Patents
Production of structural fire-retardant plastic Download PDFInfo
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- CN1294158C CN1294158C CNB2004100260151A CN200410026015A CN1294158C CN 1294158 C CN1294158 C CN 1294158C CN B2004100260151 A CNB2004100260151 A CN B2004100260151A CN 200410026015 A CN200410026015 A CN 200410026015A CN 1294158 C CN1294158 C CN 1294158C
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Abstract
The present invention relates to a production method of a structural fire-retardant plastic. The present invention is characterized in that aminated poly methylol aralkyl phenolic resin is used as the base resin of the structural fire-retardant plastic. The production method of the structural fire-retardant plastic comprises the following steps: firstly, the poly methylol aralkyl phenol resin is produced by reacting poly aralkyl phenol with formaldehyde, and then the aminated poly methylol aralkyl phenol resin of the structural fire-retardant plastic is produced by reacting the dicyandiamide with the poly methylol aralkyl phenol resin. The resin and hexamethylenetetramine as an additive, zinc stearate, white carbon black in a deposition method, non-alkali glass fiber, etc. are sufficiently immersed and dried, and then the aminated poly methylol aralkyl phenol plastic of the structural fire-retardant plastic is obtained. The oxygen index of the present invention can reach 53, and the level of vertical combustion is from FV to 0 grade.
Description
Affiliated technical field: the preparation method who the present invention relates to a kind of structure-type flame retardant plastics.The main oligopolymer of poly-methylol aralkyl phenol and the Dyhard RU 100 of adopting reacts the poly-methylol aralkyl-phenol resin of acquisition amination under base catalysis, the plastics that this kind resin is made have good flame retardant property, mechanical property, resistance toheat and have the favorable manufacturability energy.
Background technology: because the hazardness of fire is very big, so fire-retardant problem already is paid attention to by people, the application of high molecular polymer has spread to the every field of national economy, all requires fire-retardant as electrical equipment cable, material of construction, aerospace parts etc.The method of generally taking is to add fire retardant in polymkeric substance, all contains halogen in the fire retardant of plurality, and it is toxic and the intensive smothering action arranged to human body to emit hydrogen halide during burning.Most fire retardants often with dense smoke, hinders the visibility meter when rescuing in burning.It should be noted that the low toxic side effect of development afterwards, the fire retardant new variety of low cigarette, but the adding of these fire retardants also is difficult to overcome shortcomings such as making polymkeric substance resistance toheat and mechanical properties decrease, manufacturability variation.So the structure-type flame-retardant polymer of the low toxic side effect of research is one of important developing direction.Can make the structure-type flame-retardant polymer of making to satisfy the requirement of desired use properties and processing performance according to molecular designing.
Summary of the invention: for avoiding the deficiencies in the prior art part, the present invention proposes a kind of structure-type flame retardant plastics preparation method of (or claiming essential flame retardant plastics), the poly-methylol aralkyl-phenol resin of prepared amination belongs to the structure-type flame-retardant polymer of low toxic side effect, low smog, not halogen-containing in the structure, no asphyxia when pyrolysis and burning, and have good flame retardant property, mechanical property, resistance toheat and processing performance, the departments such as aviation, electrical equipment, material of construction that can be applicable to use.
Technical characterictic of the present invention is: will gather aralkyl phenol earlier and make poly-methylol aralkyl-phenol resin, to gather methylol aralkyl phenol then and generate the poly-methylol aralkyl-phenol resin of amination, the more poly-methylol aralkyl-phenol resin of amination be made the structure-type flame retardant plastics.
The method that poly-aralkyl phenol is made poly-methylol aralkyl-phenol resin is: add industrial alcohol in the reactor with whipping appts, reflux exchanger and heat-exchanger rig successively, industrial acetone, add the poly-aralkyl phenol after pulverizing again, stir and be heated to 50～55 ℃ and make its whole dissolvings, add formaldehyde and an acidic catalyst then, be heated to 70～75 ℃ of reactions 4 hours, promptly make poly-methylol aralkyl-phenol resin.
100～110 parts in the poly-aralkyl phenol of above-mentioned adding, 126～138 parts of industrial alcohols, 54～59 parts of industrial acetones, concentration is 2～2.2 parts of 33～50 parts in 37% formaldehyde and an acidic catalysts.
Adopting poly-aralkyl phenol is that raw material is under the catalysis of an acidic catalyst, make poly-methylol aralkyl-phenol resin with formaldehyde reaction, this kind resin contains a large amount of virtue nuclear, nitrogen-atoms and hydroxyl and generate a large amount of aromatization type carbon when pyrolysis and burning, form loose charcoal layer structure on the surface, can hinder the generation of heat radiation and the flammable gaseous state thing of inhibition.Nitrogen-atoms generates nitrogen and ammonia in pyrolytic process, hydroxyl produces water vapor in pyrolytic process, and these all have significant fire retardation, thereby and owing to the generation that has reduced volatile products has reduced the amount of being fuming.
The present invention at first its reaction is as follows:
N=4 in the formula～7.
The method that poly-methylol aralkyl phenol is generated the poly-methylol aralkyl-phenol resin of amination is: the poly-methylol aralkyl-phenol resin of the above-mentioned reaction mass that makes is carried out underpressure distillation, after steaming materials such as ethanol, acetone and moisture, be discharged to while hot in 65～75 ℃ the hot water and be washed till neutrality, in vacuum drying oven, under the vacuum tightness of 600mmHg and 45～50 ℃, be dried to basic constant weight again; Dried poly-methylol aralkyl-phenol resin is added in the above-mentioned reactor, add industrial alcohol, industrial acetone successively, stirring and dissolving is even, add Dyhard RU 100 again, be warming up to 70～75 ℃, under basic catalyst catalysis, reacted 3～4 hours, and obtained the poly-methylol aralkyl-phenol resin of synthetic amination.
130～140 parts of the poly-methylol aralkyl-phenol resins of above-mentioned adding, 180～193 parts of industrial alcohols, 60～65 parts of industrial acetones, 25～40 parts of Dyhard RU 100s, 2～2.2 parts of basic catalysts.
Poly-methylol aralkyl phenol reacts the poly-methylol aralkyl-phenol resin of generation amination with Dyhard RU 100 under the catalysis of basic catalyst, its reaction is as follows:
After the poly-aralkyl phenol of methylol and Dyhard RU 100 react, the characteristic absorbance district 1000～1050cm of methylol
-1Obviously weaken, illustrate that methylol has participated in reaction and can observe the characteristic absorbance zone that the sign amide group exists, 1600～1700cm among the figure simultaneously significantly in infared spectrum
-1Be the acid amides I bands of a spectrum of C=O stretching vibration form, 1500～1600cm
-1Be the acid amides II bands of a spectrum that the N-H flexural vibration form.The infrared spectrogram of the poly-methylol aralkyl phenol of amination is seen Fig. 2.
The method that the poly-methylol aralkyl-phenol resin of amination is made the structure-type flame retardant plastics is: the poly-methylol aralkyl-phenol resin of synthetic amination is added in the mixing tank, add hexamethylenetetramine more successively, Zinic stearas, precipitated silica, alkali free glass fibre mixes, floods evenly; The plastics that mix, dipping is good were hung 24 hours, be to be dried to moisture and volatile matter content content in 40～50 ℃ under 600～650mmHg to be not more than till 6% in vacuum tightness again, promptly get the poly-methylol aralkyl phenola plastics of structure-type flame retardant plastics amination, these plastics are suitable for the goods of compression molding preparation especially.
50～60 parts of the poly-methylol aralkyl-phenol resins of the amination of above-mentioned adding, 2～3.5 parts of hexamethylenetetramines, 3 parts of Zinic stearass, 10～15 parts of precipitated silicas, 30～35 parts of alkali free glass fibres.
The processing condition of compression molding are: 100～110 ℃ of following thermal pretreatment 10～15 minutes, press temperature was 170 ± 5 ℃ before the compacting, and compacting pressure is 35～40MPa, and the press time is 3min/mm, 160 ℃ of back baking processing/2hr+180 ℃/2hr+200 ℃/2hr.
Test this flame retardant of plastic performance: oxygen index is 53, and the vertical combustion rank is the FV-0 level.
Description of drawings:
Fig. 1 embodiment synoptic diagram
Fig. 2: the infrared spectra of the poly-methylol aralkyl phenol of amination
Embodiment:
Now 2 couples of the present invention are further described in conjunction with the accompanying drawings:
Embodiment 1 (umber among the embodiment is weight part):
1, in reactor, adds 126 parts of industrial alcohols with whipping appts, reflux exchanger and heat-exchanger rig, 54 parts of industrial acetones, 100 parts in poly-aralkyl phenol after adding is pulverized again, stir and be heated to 50～55 ℃ and make its whole dissolvings, add concentration then and be 33～50 parts and 2 parts an acidic catalysts of formaldehyde of 37%, be heated to 70～75 ℃ of reactions 4 hours, promptly make poly-methylol aralkyl-phenol resin;
2, above-mentioned reaction mass is carried out underpressure distillation, steam materials such as ethanol, acetone and moisture after, be discharged to while hot in 65～75 ℃ the hot water and be washed till neutrality, in vacuum drying oven, under the vacuum tightness of 600mmHg and 45～50 ℃, be dried to basic constant weight again;
3, dried poly-methylol aralkyl-phenol resin is added in the above-mentioned reactor for 130 parts, add 180 parts of industrial alcohols, 60 parts of industrial acetones, stirring and dissolving is even, add 25～40 parts of Dyhard RU 100s again, be warming up to 70～75 ℃, under 2 parts of basic catalyst catalysis, reacted 3～4 hours, carry out underpressure distillation then, to steam thing be 60 parts and be neutralized to neutrality with acetic acid.Take out behind the blowing by unmodified resin and count 50～60 parts and be added in the mixing tank, add 2～3.5 parts of hexamethylenetetramines again, 3 parts of Zinic stearass, 10～15 parts of precipitated silicas, 30～35 parts of alkali free glass fibres, mix, dipping evenly;
4, will mix, flood good plastics and hang 24 hours, be to be dried to moisture and volatile matter content content in 40～50 ℃ under 600～650mmHg to be not more than till 6% in vacuum tightness again, promptly gets the poly-methylol aralkyl phenola plastics of structure-type flame retardant plastics amination.
5, as making structure-type flame retardant plastics goods, then should carry out compression molding again, its condition of molding is 100～110 ℃ of following preheatings 10～15 minutes, and press temperature is 170 ± 5 ℃, and compacting pressure is 35～40MPa, and the press time is 3min/mm.
6, baking treatment condition in back are 160 ℃/2hr+180 ℃/2hr+200 ℃/2hr.
It is 53 that the flame retardant of plastic performance reaches oxygen index according to test, and the vertical combustion rank is the FV-0 level.
Claims (4)
1, a kind of preparation method of structure-type flame retardant plastics is characterized in that:
A, in reactor, add industrial alcohol successively with whipping appts, reflux exchanger and heat-exchanger rig, industrial acetone, add the poly-aralkyl phenol after pulverizing again, stir and be heated to 50～55 ℃ and make its whole dissolvings, add formaldehyde and an acidic catalyst then, be heated to 70～75 ℃ of reactions 4 hours, promptly make poly-methylol aralkyl-phenol resin;
B, the poly-methylol aralkyl-phenol resin of the above-mentioned reaction mass that makes is carried out underpressure distillation, after steaming materials such as ethanol, acetone and moisture, be discharged to while hot in 65～75 ℃ the hot water and be washed till neutrality, in vacuum drying oven, under the vacuum tightness of 600mmHg and 45～50 ℃, be dried to basic constant weight again; Dried poly-methylol aralkyl-phenol resin is added in the above-mentioned reactor, add industrial alcohol, industrial acetone successively, stirring and dissolving is even, add Dyhard RU 100 again, be warming up to 70～75 ℃, under basic catalyst catalysis, reacted 3～4 hours, and obtained the poly-methylol aralkyl-phenol resin of synthetic amination;
C, the poly-methylol aralkyl-phenol resin of synthetic amination is added in the mixing tank, adds hexamethylenetetramine more successively, Zinic stearas, precipitated silica, alkali free glass fibre, mix, dipping evenly; The plastics that mix, dipping is good were hung 24 hours, were to be dried to moisture and volatile matter content content in 40～50 ℃ under 600～650mmHg to be not more than till 6% in vacuum tightness again, promptly got the poly-methylol aralkyl phenola plastics of structure-type flame retardant plastics amination.
2, the preparation method of structure-type flame retardant plastics according to claim 1, it is characterized in that: 100～110 parts in the poly-aralkyl phenol of above-mentioned adding, 126～138 parts of industrial alcohols, 54～59 parts of industrial acetones, concentration is 2～2.2 parts of 33～50 parts in 37% formaldehyde and an acidic catalysts.
3, the preparation method of structure-type flame retardant plastics according to claim 1, it is characterized in that: 130～140 parts of the poly-methylol aralkyl-phenol resins of above-mentioned adding, 180～193 parts of industrial alcohols, 60～65 parts of industrial acetones, 25～40 parts of Dyhard RU 100s, 2～2.2 parts of basic catalysts.
4, the preparation method of structure-type flame retardant plastics according to claim 1, it is characterized in that: 50～60 parts of the poly-methylol aralkyl-phenol resins of the amination of above-mentioned adding, 2～3.5 parts of hexamethylenetetramines, 3 parts of Zinic stearass, 10～15 parts of precipitated silicas, 30～35 parts of alkali free glass fibres.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100260151A CN1294158C (en) | 2004-04-07 | 2004-04-07 | Production of structural fire-retardant plastic |
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| CNB2004100260151A CN1294158C (en) | 2004-04-07 | 2004-04-07 | Production of structural fire-retardant plastic |
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| CN1680488A CN1680488A (en) | 2005-10-12 |
| CN1294158C true CN1294158C (en) | 2007-01-10 |
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| CNB2004100260151A Expired - Fee Related CN1294158C (en) | 2004-04-07 | 2004-04-07 | Production of structural fire-retardant plastic |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5551560A (en) * | 1978-10-07 | 1980-04-15 | Matsushita Electric Works Ltd | Preparation of laminate |
| JP2002060586A (en) * | 2000-08-11 | 2002-02-26 | Matsushita Electric Works Ltd | Phenol resin composition and insulating substrate |
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- 2004-04-07 CN CNB2004100260151A patent/CN1294158C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5551560A (en) * | 1978-10-07 | 1980-04-15 | Matsushita Electric Works Ltd | Preparation of laminate |
| JP2002060586A (en) * | 2000-08-11 | 2002-02-26 | Matsushita Electric Works Ltd | Phenol resin composition and insulating substrate |
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