CN1102602C - Phenolic resin for low-temp foaming and its preparing process - Google Patents
Phenolic resin for low-temp foaming and its preparing process Download PDFInfo
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- CN1102602C CN1102602C CN 00111275 CN00111275A CN1102602C CN 1102602 C CN1102602 C CN 1102602C CN 00111275 CN00111275 CN 00111275 CN 00111275 A CN00111275 A CN 00111275A CN 1102602 C CN1102602 C CN 1102602C
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Abstract
The present invention relates to a preparation method of low-temperature foamed phenolic resin. In the method, the molar ratio of phenol to formaldehyde is 1:1.30 to 1.80, and the formaldehyde is put into the reaction in two batches. Firstly, the phenol and part of the formaldehyde are previously polymerized by condensation in the presence of organic acid; secondly, an alkali catalyst is put in to carry out a high-temperature condensation reaction; thirdly, stable and transparent highly ortho-phenolic resin is synthesized through the addition of the formaldehyde and dehydration by distillation at reduced pressure. The resin prepared by the present invention, which is dissolved in water, can be foamed and completely cured at the temperature of 0DEG C without carrying out other kinds of post-treatment. The present invention has the advantages of energy source saving, foaming technology simplification, convenient site construction, convenient field operation, wide application ranges, obvious economic benefits and obvious social benefits.
Description
The present invention relates to foaming and use the resol production technical field, more specifically say so about the production technology of the resol that is used for low-temp foaming.
Phenolic foam material, because of its good heat resistance, shrinkability at low temperatures is little, not embrittlement, and anti-burning, low smokiness causes people's attention during burning.All oneself is used widely in engineering fields such as building, insulation, transportation, machinery, oil and chemical industry.Phenolic foam material generally can also can be made by heat-reactive phenolic resin (Resol) by the hot manufactured of novolac resin (Novolac).Adopt the latter, can heat foamable, also can accomplish the room temperature foaming.But the room temperature that it is carried out foaming all needs more than 15 ℃, is lower than 15 ℃ and then can not carries out foaming.Therefore, it can only be processed in factory building, can not carry out in-situ processing in the open air, brings very big inconvenience to unit in charge of construction.
Tracing it to its cause, mainly is the reactive modified phenolic resin poor activity of existing foaming usefulness, can only be activated under higher room temperature, and the polycondensation crosslinking reaction takes place.Because this reactive modified phenolic resin poor activity, not only can not realize the crosslinking reaction of low temperature (under 0 ℃), and implement the required solidifying agent usage quantity of crosslinking reaction more than 15～20%, abroad also need more than 12%, thereby also improved the real cost of froth product.
In addition, in order to make froth product have satisfied physical and mechanical property, behind foaming, also need under 80 ℃～100 ℃, to be cured aftertreatment in the prior art, not only expended a large amount of energy, and further increased the cost of froth product again.
In existing synthetic technology, the gel time of resin is shortened, can improve the activity of resol, but the problem of bringing is: 1. the package stability of resin reduces greatly, and what have can only put a week, and not adding solidifying agent just can gel.2. resin viscosity is too big, be difficult to construction, and Pao Mo Kong Liao is inhomogeneous.The simple formaldehyde charging capacity that improves also can improve the reactive behavior of resin, but make that thus synthetic resin branching is serious, and cross-linking density is excessive, and the fragility of the porous plastics of making increases, use properties (particularly shock resistance) variation.
The rapid shaping phenolic molding powder that uses in the prior art is a kind of high adjacent resol, and it has high reaction activity and high (referring to J.polym.sci 22.477 (1956); The clear 35-13696 of Japan's special permission).But the high adjacent position phenolic resin of this purposes generally all is pure dissolubility, or solid-state, and such resin is unsuitable for the room temperature foam process.So up to the present do not see the report of the high adjacent position phenolic resin that is useful on the room temperature foaming as yet.
The resol and the production technology thereof that the object of the present invention is to provide a kind of high reactivity to foam at low temperatures.
As the resol of room temperature foaming, at first should be a kind of water base property liquid resin.Realize low-temp foaming, make it at a lower temperature (about 0 ℃) and can fully carry out crosslinked polycondensation, must improve the reactive behavior of water base property resol.
For achieving the above object, the present invention has synthesized a kind of structural formula and is:
Has high reaction activity and high, high adjacent position phenolic resin that simultaneously again can be water-soluble.This resin has shown following physicochemical characteristic: outward appearance is the liquid of stable transparent, and its number-average molecular weight is 350-400, and viscosity is 0.5-2.0PaS, water soluble, the used water infinite dilution, functionality is (2.4-2.8), gel time is 110s/150 ℃ of g, can solidify 0 ℃ of foaming.
The present invention in experimental study, solved simultaneously resin send out should be active, water-soluble, four main difficult problems such as viscosity and molecular weight.It is 37% formaldehyde, 0.5～2.0 part organic acid and the water-soluble high adjacent position phenolic resin of 0.3～5.0 part of a kind of stable transparent of basic catalyst reaction generation that its ratio of components of the said high adjacent position phenolic resin of the present invention (in weight part) adds 100～200 parts of content with respect to 100 parts of phenol.
A key character of the present invention is that the phenol of synthetic this high adjacent position phenolic resin and the mol ratio of formaldehyde are 1: 1.30～1.80mol, is much higher than the phenol in the common resol and the mol ratio of formaldehyde, (common mol ratio is 1: 1.15～1.25).Improve the formaldehyde consumption and help the active and water miscible raising of resin reaction, and reduce the free phenol in the resin, the reduction of free phenol also helps improving the activity of resol.But high formaldehyde proportioning is unfavorable for the ortho position addition of phenol and formaldehyde, and causes increasing the weight of of resin branching, and the present invention adopts the method that in batches adds formaldehyde in the resin building-up process for this reason, balance the two contradiction.
Another key character of the present invention is that said high adjacent position phenolic resin is to carry out polycondensation under the effect of a kind of quaternary complex catalyst system.Said complex catalyst system comprises organic acid, and it can be formic acid, acetate or oxalic acid, the oxyhydroxide of alkaline earth metal, and it can be (Ba (OH) 2, Mg (OH) 2 or Ca (OH) 2; The alkaline earth metal oxide compound, it can be MgO, BaO, CaO; And the alkaline earth metal organic acid salt that reacts to each other and generate by acid, alkali, as formic acid barium salt or acetate magnesium salts etc.Wherein the oxyhydroxide of alkaline earth metal and oxide compound are to become a kind of form of compound basic catalyst to add with mutual combined crosswise, and its combination is than being 3: 2 to 10: 1.As combinations such as Ba (OH) 2+CaO, Ba (OH) 2+MgO, Ca (OH) 2+MgO, Ca (OH) 2+BaO, Mg (OH) 2+BaO or Mg (OH) 2+CaO.Can certainly use the molectron of single alkaline earth metal oxyhydroxide and oxide compound thereof, use this molectron can reduce consumption, its consumption is less than 2%.The adding of alkaline earth metal oxide compound can also improve the viscosity of resin.
Resin of the present invention is to obtain by following synthesis technique, and it comprises following important step:
1. phenol mixes with first part of formaldehyde earlier, and the input amount of formaldehyde is 70～90% of its total amount, adds organic acid, and control PH is 5～5.5, carries out the precondensation reaction under 40～60 ℃.Then add basic catalyst, stir and heat up, under 95～105 ℃, carry out the high-temperature polycondensation reaction;
2. drop into second part of remaining formaldehyde again, make the feed ratio of phenol and formaldehyde reach 1.30～1.80mol, reduce temperature of reaction and continue reaction down for 80～90 ℃;
3. input aminocompound, under low vacuum, reaction and dehydration are proceeded in underpressure distillation, and vacuum tightness is 10～25Kpa, and distillation temperature is 60～80 ℃;
4. the input table surface-active agent obtains product behind the mixing.
It can also be seen that from above-mentioned synthesis technique another key character of the present invention is to synthesize the said high adjacent position phenolic resin of the present invention by four-step reaction.
(1) carries out prepolymerization reaction under the acidic conditions, in the suitable reaction times, make phenol and formaldehyde generate some low molecular Novolac resins.
(2) in the presence of basic catalyst, carry out the high-temperature alkaline condensation reaction, addition formaldehyde on low molecular Novolac molecular resin, the oligopolymer of formation thermoset (Resol) resol.High temperature helps the ortho position addition reaction and the polycondensation of formaldehyde, makes to form
The reaction rate accelerates of structure.
(3) after adding formaldehyde, carry out in temperature reaction.Help the reduction of free phenol after adding formaldehyde, and make a certain amount of branched structure of resin formation, have suitable viscosity.
(4) low-temp reaction is carried out in underpressure distillation under low vacuum, and dehydration makes polycondensation be tending towards finishing.In this section reaction,, help reaction and finish owing to take off the water of raw material and reaction process generation.Resin solid content increases simultaneously, has improved the viscosity of resin.
The control of above-mentioned four-step reaction time also is an important factor, for example high-temperature alkaline condensation reaction, and overlong time can form ehter bond, makes the water-soluble variation of resin, can not foam; Time is too short, then in the resin ortho position structure very little, the resin reaction poor activity then can not low-temp foaming and curing.So the best relative proportion of above-mentioned four-step reaction time is: 1: 1: 3: 3.
Another feature of the present invention is the aminocompound that has also added 1～10 weight part in four-step reaction with respect to the phenol of 100 weight parts, and has added the tensio-active agent of 2～10 weight parts in final product.
Adding aminocompound in this reaction process, is in order to reduce the free formaldehyde in the product, to improve the stability of product.But and the reactive behavior of equalizing and buffering resin, make convenient, the may command of foam process, improve the use properties of resin.Said aminocompound can be selected from quadrol, diethyl triamine, polyethylene polyamine, aniline or trimeric cyanamide.So the content of free aldehyde can be reduced to below 1% in the final product that obtains.
The tensio-active agent that adds in the production technique of the present invention is a kind of anion surfactant.As Witco 1298 Soft Acid, oleic acid, sodium oleate, perhaps polysorbas20,40,60,80, this class 80, commercially available nonionogenic tenside such as op-10 all can be selected for use.Add tensio-active agent and can improve resin dispersion and water-soluble.Make when resin expanded, the abscess of formation is uniform and stable, and helps the raising of package stability.
By synthetic resol of the present invention, quality product meets following requirement:
Solid content:＞80%
PH ：＞7.5
Gel time: 150 ℃, 100～80 seconds (gram)
Free aldehyde:＜1%
Free phenol:＜9%
Use the resin material that resin of the present invention can be used as low-temp foaming, its blowing temperature also can normally foam at 0 ℃, solidify less than 15 ℃.Can certainly be used for room temperature foaming, curing more than 15 ℃, at this moment, required whipping agent and solidifying agent still less for example 25 ℃ of foaming down, only need the whipping agent of 5% solidifying agent and 1～1.5%.
Because resin reaction of the present invention is active high, hardener dose required in foam process is few, and its usage quantity has only 1/2～1/3 of common resol.And get final product completion of cure under the low temperature, also need not to carry out again aftertreatment.Both reduce tooling cost, also improved the product performance of foam material.
Table 1 has been enumerated the present invention and the performance contrast of froth product both at home and abroad, and the froth product performance of resin of the present invention meets the quality standard of existing phenolic foam products fully as can be seen from the table.
Table 1 the present invention and froth product performance contrast both at home and abroad
| Project | The present invention | Thermo-cor | Domestic phenolic foam products standard |
| Apparent density Kg/m3 | 40～60 | 50 | 40～60 |
| Ultimate compression strength Kpa | 130～160 | 140 | ＞100 |
| Thermal conductivity w/m.k | 0.025～0.035 | 0.032 | ＜0.035 |
| Dimensional change % | 150℃.2h-2 | 70 ℃, 28 days-7 | |
| Flame retardant resistance | Naked light does not fire | Naked light does not fire | Naked light does not fire |
| Oxygen index | 53 | ＞35 | |
| Water-intake rate | 2～3 | ＜4 | |
| Resistant of high or low temperature | -60～-200℃ | -60～-190℃ |
With a concrete instance production technique of the present invention is described further again below:
Earlier be that 37% formaldehyde drops in the reactor, stir adding methyl alcohol 50kg and acetic acid 14kg after 15 minutes the phenol of 1000kg and 1120kg concentration.After being warming up to 40 ℃ under stirring, keeping after 30 minutes and add Ca015kg.Restir is warming up to 100～102 ℃, reacts after 1 hour, is cooled to 90 ℃, adds formaldehyde 280kg, continue reaction after 1 hour, the gel time under 150 ℃ of the sampling and measuring is when reaching 110 seconds, make system in underpressure distillation, pressure is 10～25Kpa, and controlled temperature is below 75 ℃.Water by metering steams calculates the solids content in the reactant, when solids content reaches 70%, adds quadrol 50kg, continues reaction under reduced pressure to reaching technical indicator, adds tween (20) 60kg, mixing.Make product 1650kg.
Product meets following index:
Gel time: 150 ℃, 100～80 seconds (gram)
Solids content:＞80%
PH ：＞7.5
Free phenol:＜9%
Free aldehyde:＜1%
With the above production of resins phenol formaldehyde foam of the present invention that makes: get resin 1000 grams of the present invention, behind the fluoro trichloromethane 20 gram mixings, under agitation add 6 gram tosic acid, thorough mixing 20 seconds, be cast in the mould, beginning the reaction foaming under 5～15 ℃ after through 2～3 minutes.Foaming was finished in 1 minute, and curing reaction can be finished in 2～3 minutes.The phenolic foam products that makes meets the described index of table 1.
Different with mixed batch and proportioning according to envrionment temperature, mixing time, reaction times and curing cycle all may be different, and foam density is relevant with foaming agent consumption.In order to make 30kg/m
3With the porous plastics of lower density, can in resin, add suitable quantity of water, adjust viscosity.Or water and solidifying agent mixed afterwards earlier add.
Advantage of the present invention is clearly, but compares with existing foamed phenolic resin, and resin of the present invention can be in 0 ℃ of foaming, curing.Thus, under most weather condition, all can construct when envrionment temperature is low.Because resin reaction of the present invention is active high, the consumption of required solidifying agent is few in the foam process, has reduced tooling cost, and low temperature (more than 0 ℃) can foam down, completion of cure, need not to remake aftertreatment (as heat treated etc.) and both can save the energy, also simplified operating procedure.Thereby can carry out site operation and field work, enlarged range of application.As the site operation of field pipeline insulation, construction work etc., also can in mould, make various section bars.The fire-retardant heat-insulation material that can be widely used in transport trade, construction industry, petrochemical industry and other industries has tangible economic benefit and social benefit.
The invention will be further described to use several examples below again, never only is defined in certainly among these several embodiment.(following umber is all in weight part)
Embodiment 1 (prescription 1)
100 parts of phenol, 128 parts in formaldehyde, suction feeding is added in the reactor of tool stirring, backflow, heating and cooling.Stir after 15 minutes and to add 1 part of 7 parts of methyl alcohol and acetic acid.Stir afterwards down and slowly be warming up to 40 ℃, keep reaction and add 4 parts of CaO after 30 minutes, be warming up to 100～102 ℃ under stirring.Reaction was carried out 1 hour under this temperature, was cooled to 90 ℃ afterwards, added 32 parts of formaldehyde, continued reaction.After reaction was carried out 1 hour, the gel time of sampling and measuring below 150 ℃ when reaching 110 seconds, under reduced pressure reacted system, and temperature is controlled at below 75 ℃.Vacuum tightness is 15KPa.By the water that metering steams, the solids content of counting system when solids content reaches 70%, adds 5 parts of quadrols, continues the decompression reaction to reaching technical indicator, adds (20) 8 parts of tweens, blowing, product.
Embodiment 2 (prescription 2)
Operation is by example 1, and catalyst acetic acid is used formic acid instead in the prescription, and CaO uses Ba (OH) instead
2With the CaO mixed system.100 parts of phenol, 200 parts in formaldehyde, 7 parts of methyl alcohol, 0.5 part in formic acid, Ba (OH)
23 parts, 2 parts of CaO, tensio-active agent index tween (20) consumption is increased to 10 parts, and the quadrol add-on is 6 parts.But by the synthetic foamed phenolic resin of example 1 operation.
Embodiment 3 (prescription 3)
Operation is by example 1, and catalyzer CaO uses Ba (OH) instead in the prescription
23 parts, 2 parts in magnesium oxide, other synthesize foamed phenolic resin with example 1 but press example 1 operation.
Embodiment 4 (prescription 4)
By example 1, CaO uses Ba (OH) instead in the prescription by operation in operation
2, 5 parts of consumptions, other synthesize foamed phenolic resin with example 1 but press example 1 operation.
Embodiment 5 (prescription 5)
Operation is by example 1, and other are constant in the prescription, only change the formaldehyde consumption.The formaldehyde total amount is 100 parts, adds 90 parts for the first time, adds 10 parts for the second time.
Embodiment 6 (method for making 1)
By the prescription that example 3 provides, control reaction temperature and time.Make 95～105 ℃ down reaction carried out 40 minutes, add second part of metering formaldehyde when being cooled to 85 ℃ after, make 85 ℃ down reaction carry out, 100 minutes, the following 65 ℃ of reactions 120 minutes of reducing pressure.
Embodiment 7 (method for making 2)
By the prescription that example 3 provides, control level of response and time.Make 95～105 ℃ down reaction carried out 1 hour, adds second batch of formaldehyde after, 80 ℃ of reactions 3 hours down, decompression low temperature (60 ℃) reacted 3 hours down.And pre-reaction time is 1 hour under the acidic conditions.But the synthetic foamed phenolic resin has better comprehensive performance under this condition.
Embodiment 8 (method for making 3)
By the prescription that example 3 provides, control reaction temperature and time.After reaction was carried out 30 minutes under 95～105 ℃, 90 ℃ added second part of formaldehyde down, and 90 ℃ were reacted 1.5 hours, and reaction is 1.5 hours under 70 ℃ of decompressions, and the synthetic resin viscosity is less under this condition.
Claims (10)
1. production method that is used for the resol of low-temp foaming, mainly by phenol, formaldehyde under the basic catalyst effect, make through polycondensation, it is characterized in that phenol and formaldehyde synthesize with 1: 1.30～1.8 mol ratios, formaldehyde drops into reaction in two batches, phenol and first part of formaldehyde carry out earlier the low temperature prepolymerization reaction in the presence of organic acid, then add second part of formaldehyde and carry out middle temperature reaction, low-temp reaction is proceeded in underpressure distillation under low vacuum again, obtains a kind of water soluble resin of stable transparent.
2. according to the described production method of claim 1, said phenol, the polycondensation of formaldehyde under organic acid, basic catalyst effect, it is characterized in that its ratio of components (in weight part) is: with respect to 100 parts of phenol, adding 100～220 parts of content is 37% formaldehyde, 0.5～2.0 part organic acid and the water soluble phenol resin of 0.3～5.0 part of a kind of stable transparent of basic catalyst reaction generation.
3. according to claim 1 or 2 described production methods, it is characterized in that said organic acid is to be selected from formic acid, acetate or oxalic acid.
4. according to claim 1 or 2 described production methods, it is characterized in that said basic catalyst is the oxyhydroxide of Ca, Ba, Mg and the compound basic catalyst that the basic oxide combined crosswise forms thereof, the portfolio ratio of its oxyhydroxide and basic oxide (in weight part) is 3: 2～10: 1.
5. according to the described production method of claim 2, it is characterized in that in the product phenol with respect to 100 weight parts, also added the aminocompound of 1～10 weight part, said aminocompound is selected from quadrol, diethyl triamine, polyethylene polyamine, aniline or trimeric cyanamide.
6. according to the described production method of claim 2, it is characterized in that also having added with respect to the phenol of 100 weight parts in the final product anion surfactant or the nonionogenic tenside of 2～10 weight parts.
7. according to the described production method of claim 1, it is characterized in that comprising following key step:
7-1 phenol mixes with first part of formaldehyde earlier, and the input amount of formaldehyde is 70～80% of its total amount, adds organic acid control PH 5～5.5, carries out the precondensation reaction under 40～60 ℃.
7-2 then adds basic catalyst, stirs to heat up, and carries out the precondensation reaction at 95～105 ℃.
7-2 drops into second part of remaining formaldehyde again, reduces temperature of reaction and continues reflection down at 80～90 ℃.
7-3 drops into aminocompound, and underpressure distillation continues reaction and dehydration down, and its vacuum tightness is 10～15Kpa, and distillation temperature is 60～80 ℃.
7-4 input table surface-active agent, mixing obtains this product.
8. according to the described production method of claim 7, it is characterized in that the relative proportion in its reaction times is 1: 1: 3: 3 in 7-1,7-2,7-3 and 7-4 four steps building-up reactions.
9. the resol of making according to the production method of claim 1 is characterized in that at said resol it being that a kind of structural formula is
High adjacent position phenolic resin, this resin shows below physicochemical characteristic:
(1) outward appearance: the liquid of stable transparent
(2) molecular weight: 350～400
(3) viscosity: 0.5～2.0PaS
(4) solubleness: water-soluble, the used water infinite dilution
(5) gel time: 110s/150 ℃ g
(6) can be in 0 ℃ of foaming, curing
(7) functionality is 2.4～2.8
10. the described resol of claim 9, as the resin material of low-temp foaming, its blowing temperature is less than 15 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00111275 CN1102602C (en) | 2000-08-10 | 2000-08-10 | Phenolic resin for low-temp foaming and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00111275 CN1102602C (en) | 2000-08-10 | 2000-08-10 | Phenolic resin for low-temp foaming and its preparing process |
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| Publication Number | Publication Date |
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| CN1282746A CN1282746A (en) | 2001-02-07 |
| CN1102602C true CN1102602C (en) | 2003-03-05 |
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| CN 00111275 Expired - Fee Related CN1102602C (en) | 2000-08-10 | 2000-08-10 | Phenolic resin for low-temp foaming and its preparing process |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393764C (en) * | 2003-06-27 | 2008-06-11 | 上海尖端工程材料有限公司 | Foam type phenol-formaldehyde resin and its production technology |
| CN1955206B (en) * | 2005-10-28 | 2013-03-20 | 苏州美克思科技发展有限公司 | Synthesis of low normal temperature foamable phenolic resin and method for preparing phenolic foam |
| NL2006218C2 (en) * | 2011-02-16 | 2012-08-24 | Trespa Int Bv | A method for reducing the formaldehyde content of a resinous starting material. |
| CN105315481B (en) * | 2015-11-30 | 2018-08-14 | 赤峰富龙市政公用工程有限责任公司 | A method of preparing flame retardant type phenolic resin low temp expanded material |
| CN107083017A (en) * | 2017-06-14 | 2017-08-22 | 济南大学 | A kind of normal temperature can send out synthesis and the foaming method of phenolic resin |
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