CN104448698B - A kind of melamine formaldehyde molding compound and preparation method thereof - Google Patents
A kind of melamine formaldehyde molding compound and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of melamine formaldehyde molding compound and preparation method thereof, uses boron modification melamine resin as matrix resin, adds reinforcing fiber, inorganic filler and auxiliary agent, prepares melamine formaldehyde molding compound by mediating with plasticating technology.The melamine formaldehyde molding compound that the present invention prepares has excellent heat resistance and dimensional stability and preferably mechanical performance.
Description
Technical field
The present invention relates to Polymer Synthesizing and technical field of modification, a kind of melamino-formaldehyde molding
Material and preparation method thereof.
Background technology
Melamine formaldehyde molding compound is a kind of high-performance composite materials, and it is to be with melamine resin
Matrix, with organic or inorganic filler as reinforcement, adds each analog assistant, prepared by certain plasticizing process and
Come.The performance of resin matrix has important impact to the performance of moulding compound, compared with phenolaldehyde moulding compound, by
It is colourless transparent resin in melamino-formaldehyde matrix resin, all kinds of light color moulding compound, resulting product can be prepared
Bright, has good anti creepage trace performance, and the most mold compound curing process produces without ammonia, because of
This relatively phenolaldehyde moulding compound has many prominent advantages.But the fragility of melamine formaldehyde molding compound is big, toughness
Difference, and low compared with the thermostability of phenolaldehyde moulding compound, low with the goods heat distortion temperature obtained by equivalent material
20～50 DEG C, therefore the application in some heat-resisting fields is subject to certain restrictions.
The Chinese patent of Publication No. CN101585953B discloses the system of a kind of melamine formaldehyde molding compound
Preparation Method, is 6～10 with the pH of sodium hydroxide regulation formaldehyde, adds tripolycyanamide and modifying agent after intensification,
It is continuously heating to 80～90 DEG C, after reacting 1～3 hour, addition formaldehyde catching agent and triethanolamine, vacuum dehydration,
Then mediate 15～60 minutes to obtain wet feed with reinforcing material, after vacuum drying, obtain siccative, siccative and inorganic filler
And releasing agent ball milling 10～30 hours in ball mill, obtain melamine formaldehyde molding compound.Modifying agent is poly-
One or more in vinyl alcohol, Polyethylene Glycol, para toluene sulfonamide, dicyandiamide and benzoguanamine
Arbitrarily ratio mixing, modified moulding compound toughness improves, and burst size of methanal reduces, but this moulding compound thermostability
Not enough.
The Chinese patent of Publication No. CN1323113C discloses a kind of high-performance melamine-phenol-formaldehyde
Moulding compound, with tripolycyanamide-P-F copolymer resins or melamine formaldehyde resin/phenol-formaldehyde resin
Blend is matrix resin, select inorfil and organic fiber be reinforcing agent, inorganic mineral be filler, adopt
It is prepared for injection-type tripolycyanamide-P-F (MP) moulding compound, this molding with composite crosslinking curing system
Material has higher heat distortion temperature (190 DEG C), compares proof tracking index (CTI) (600V) and relatively
Good arc resistance can (180 seconds), fire resistance (UL94V-0@0.8mm).But the thermostability of this material
Still being unable to reach under equal conditions the phenolaldehyde moulding compound of preparation, meanwhile, the thermostability of phenolaldehyde moulding compound also also has
Treating to improve further, such as CN101665613B provides the phenolaldehyde moulding compound of a kind of high-temperature baking resistant, bag
Containing additive, also include phenolic resin, wood powder, mineral filler, hexamethylenamine, phosphoric anhydride, acrylate
Nanoparticle or silicon rubber nano particle, and disclose the preparation method of the phenolaldehyde moulding compound of high-temperature baking resistant,
Phenolaldehyde moulding compound prepared by this invention do not ftractures 250 DEG C of bakings for 2 hours, non-foaming, indeformable.
Therefore, the thermostability of melamine formaldehyde molding compound prepared by employing prior art need to carry further
High.
Summary of the invention
The technical problem to be solved is to provide a kind of thermostability with excellence and dimensional stability
Melamine formaldehyde molding compound and preparation method thereof.
In order to solve above-mentioned technical problem, the technical solution used in the present invention one is:
A kind of melamine formaldehyde molding compound, including the component of following weight portion:
The structural formula of described boron modification melamine resin is as follows:
In formula, R1" and R2" it is the most equal organic substituent；
R1′、R2' and R3' it is independently selected from H or CH2OH or following group:
And R1′、R2' and R3' at least one be following group:
R1、R2……R5It is independently selected from H or CH2OH or following group:
In order to solve above-mentioned technical problem, the technical solution used in the present invention two is:
The preparation method of a kind of melamine formaldehyde molding compound as above, comprises the following steps:
(1) mediate: weigh described boron modification melamine resin, reinforcing fiber, inorganic filler,
Firming agent, accelerator, coupling agent and releasing agent, mediate 20～40 minutes at a temperature of 60～80 DEG C, obtains all
Even compound；
(2) plasticate: the compound using double roller mill to obtain step (1) is plasticated, mill
Before machine, roll temperature is 80～110 DEG C, and rear roll temperature is 130～150 DEG C, and the time of plasticating is 10～20 minutes,
To melamine formaldehyde molding compound.
The beneficial effects of the present invention is:
Melamine formaldehyde molding compound provided by the present invention, tool compared with common melamine formaldehyde molding compound
Having excellent thermostability and dimensional stability, the fragility of molding product is also improved.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, give below in conjunction with embodiment
With explanation.
The design of most critical of the present invention is: use boron modification melamine resin as matrix resin,
Owing to boron modification melamine resin containing flexible B-O key, branched structure and the boron of high bond energy
Existing, therefore thermostability, toughness and anti-flammability are far above common melamine resin, for preparation three
The adhesion strength of moulding compound, crosslink density and thermostability can be significantly improved during melamine-formaldehyde moulding compound, with
Common melamine formaldehyde molding compound is compared has excellent thermostability and dimensional stability, molding product
Fragility is also improved.
Concrete, the melamine formaldehyde molding compound of embodiment of the present invention, including the component of following weight portion:
The structural formula of described boron modification melamine resin is as follows:
In formula, R1" and R2" it is the most equal organic substituent；
R1′、R2' and R3' it is independently selected from H or CH2OH or following group:
And R1′、R2' and R3' at least one be following group:
R1、R2……R5It is independently selected from H or CH2OH or following group:
Knowable to foregoing description, the beneficial effects of the present invention is: melamino-formaldehyde provided by the present invention
Moulding compound, has excellent thermostability and dimensional stability, mould compared with common melamine formaldehyde molding compound
The fragility of plastic is also improved.
Further, the following formula I of structural formula of described boron modification melamine resin, (II), (III)
Or shown in (IV):
In formula, R1′、R2′……R9' it is independently selected from H or CH2OH or following group:
And R1′、R2′……R9In ' at least one be following group:
R1″、R2″……R5" it is independently selected from H or CH2OH or following group:
Further, described reinforcing fiber is selected from carbon fiber, basalt fibre, polyester fiber, aluminium oxide fibre
One or more in dimension, wood powder, paper powder, bamboo powder and glass fibre.Reinforcing fiber is to undertake the master of external force
Body, can improve the mechanical performance of moulding compound.
Further, described inorganic filler is selected from calcium carbonate, Pulvis Talci, mica powder, wollastonite powder and flake asbestos
In one or more.Inorganic filler can improve moulding compound mechanical performance, thermostability and processing fluidity.
Further, described firming agent one or many in hexamethylenamine, triethylamine and p-methyl benzenesulfonic acid
Kind.The addition of firming agent can make described boron modification melamine resin solidify, between little molecule mutually
Connect, form macromolecular chain so that melamine formaldehyde molding compound goods form cross-linked structure, improve molding
The mechanical performance of material products and insulating properties.
Further, during described accelerator is selected from calcium oxide, magnesium oxide, calcium hydroxide and magnesium hydroxide
Plant or multiple.Accelerator can improve solidification rate, reduces solidification temperature, reduces hardener dose.
Further, described coupling agent selected from titanate coupling agent, aluminate coupling agent, silane coupler,
One or more in boric acid ester coupler and phosphate coupling agent.Coupling agent is interface modifier, can improve
Boron modification melamine resin and inorganic filler and the interface performance of reinforcing material, make inorganic filler and increasing
Strong material reaches preferably to disperse, and mechanical performance and the thermostability etc. improving molding product are all had good effect
Really.
Further, described releasing agent is in stearic acid, calcium stearate, magnesium stearate and aluminium stearate
One or more.Releasing agent can prevent melamine formaldehyde molding compound to be bonded to abrasive surface.
Concrete, the preparation method of the melamine formaldehyde molding compound of embodiment of the present invention, including following step
Rapid:
(1) mediate: weigh described boron modification melamine resin, reinforcing fiber, inorganic filler,
Firming agent, accelerator, coupling agent and releasing agent, mediate 20～40 minutes at a temperature of 60～80 DEG C, obtains all
Even compound；
(2) plasticate: the compound using double roller mill to obtain step (1) is plasticated, mill
Before machine, roll temperature is 80～110 DEG C, and rear roll temperature is 130～150 DEG C, and the time of plasticating is 10～20 minutes,
To melamine formaldehyde molding compound.
Additionally, present invention also offers a kind of preparation method of above-mentioned boron modification melamine resin:
First organoboron compound is reacted in the basic conditions with formaldehyde the methylolated organic boron of generation, then will
Methylolated organic boron generates boron modification melamine resin, institute with formaldehyde, tripolycyanamide copolycondensation
The structural formula stating organoboron compound is as follows:
Wherein, R1And R2For the most equal organic substituent.
The preparation method principle of above-mentioned boron modification melamine resin is as follows:
Organoboron compound first with formaldehyde generation substitution reaction, in organoboron compound connect on multiple hydroxyls
Methyl, the substituted organic boron of methylol will be with during the synthesis and solidification of melamine resin
Chemical bond mode is connected in the strand of melamine resin.Such as, using triphenyl borine acid esters as
When melamine resin is modified by organoboron compound, the phenyl ring on triphenyl borine acid esters contains work
Property site, can with formaldehyde generation polycondensation reaction generate methylol, it is possible to methylol react generate methylene,
In melamine resin synthesis and solidification process, triphenyl borine acid esters and formaldehyde react the hydroxyl first generated
Base can further with the amino on tripolycyanamide or the methylol generation polycondensation reaction on melamine resin,
Triphenyl borine acid esters is connected in the strand of melamine resin in chemical bond mode the most at last；And for example,
Using diphenyl-borinic acids-2-amino ethyl ester as organoboron compound melamine resin is modified time,
Phenyl ring and amino in diphenyl-borinic acids-2-amino ethyl ester are active group, also will be with chemical bond side after reaction
Formula is connected on the strand of melamine resin.Whether triphenyl borine acid esters or diphenyl-borinic acids
-2-amino ethyl ester, all contains flexible B-O key in the strand of the organoboron compound meeting present configuration,
Bond energy (774.04kJ/mol) due to B-O key is higher than the bond energy (334.72kJ/mol) of C-C key, therefore
The thermostability of the boron modification melamine resin prepared is far above common melamine resin,
Flexible B-O key also can reduce the fragility of resin；In cured product, the three-dimensional cross-linked network structure of boracic, makes boron
The ablation resistance of modified melamine-formaldehyde resin and resistance to neutron irradiation performance are also superior to general tripolycyanamide
Formaldehyde resin；Further, since the existence of boron, boron modification melamine resin can in cracking process
Improve the structure of coke, i.e. form the vitreous carbon with compact texture, and vitreous carbon can effectively stop oxygen to enter
Enter inside resin, thus inhibit the further burning of boron modification melamine resin, therefore the resistance of resin
Combustion property is improved.
When organoboron compound is triphenyl borine acid esters, primary response formula is as shown in (1):
When organoboron compound is diphenyl-borinic acids-2-amino ethyl ester, primary response formula is as shown in (2):
In the reaction equation shown in above-mentioned (1) and (2), R1、R2……R9Be independently selected from H or
CH20H, and R1、R2……R9It is not all H；R1′、R2′……R9' be independently selected from H or
CH20H or following group:
And R1′、R2′……R9In ' at least one be following group:
R1″、R2″……R5" it is independently selected from H or CH2OH or following group:
Tripolycyanamide, triphenyl borine acid esters and diphenyl-borinic acids-2-amino ethyl ester can contract with formaldehyde respectively
Poly-reaction, generates a replacement respectively to hexabasic tripolycyanamide, a replacement to nine substituted triphenyl boric acid
Ester and a replacement are to eight substituted diphenyl-borinic acids-2-amino ethyl esters.The substituted melamine generated and replacement three
Can lead between phenyl boronate and between substituted melamine and substituted diphenyl-borinic acids-2-amino ethyl ester
Cross methylene or dimethylene ether is connected, obtain boron modification melamine resin.The replacement three generated
Between poly cyanamid, replace between triphenyl borine acid esters and also may be used between substituted diphenylamine ylboronic acid-2-amino ethyl ester
To be connected by methylene or dimethylene ether.
Compared with the preparation method of existing melamine resin, the present invention uses the organic of special construction
Melamine resin is modified preparing boron modification melamine resin, at trimerization by boron compound
Introducing B-O key in cyanamide formaldehyde resin, improve the crosslink density of resin after solidification, the thermostability of resin obtains
To significantly improving, the ablation resistance of resin, resistance to neutron irradiation performance and fire resistance are also improved.
Further, the preparation method of the boron modification melamine resin of the present invention, comprise the steps:
1) formaldehyde of organoboron compound and excess is added in reactor, stir, with alkali regulation reaction
The pH of liquid is 8-10, is warming up to 80-120 DEG C, reacts 1-4h；
2) to step 1) reactant liquor of gained adds tripolycyanamide, stir and react 1-6h, obtaining boron and change
Property melamine resin.
Further, described organoboron compound is preferably triphenyl borine acid esters, diphenyl-borinic acids-2-amino second
One or more in ester, L-norvalyl diphenyl-borinic acids ester, L-cysteinyl-diphenyl-borinic acids ester.
Further, described formaldehyde is preferably the formalin of mass concentration 30%～50%, the most excellent
Elect the formalin of 35%～45% as.
Further, the vacant adjacency pair position on the phenyl ring of organoboron compound is respectively provided with activity, and too high is organic
Boron compound consumption, by making the molecular weight of boron modification melamine resin prepared bigger than normal, reacts the most easily-controllable
System, will crosslink the consequence of solidification time serious, be unfavorable for industrialized production, and therefore the present invention is the most organic
The consumption of boron compound is the 5%～40% of tripolycyanamide quality, more preferably 10%～30%.
Further, in step 1) in, reaction temperature is preferably 80～100 DEG C, more preferably 85～95 DEG C.
Further, in step 2) in, the substituted organic boron of methylol, residual formaldehyde are carried out with tripolycyanamide
Copolyreaction synthesis boron modification melamine resin, reaction temperature is preferably 80～100 DEG C, the most excellent
Electing 90～100 DEG C as, the response time is preferably 1～6h, and reaction end can be with cloud point as foundation, in order to obtain
The resin of higher molecular weight, can continue to reaction after arriving cloud point, after arriving the predetermined extent of reaction, and can
Directly to use, it is also possible to carry out dehydration as required and obtain the boron modification melamino-formaldehyde tree that solid content is high
Fat, dehydration number can be to need the solid content that reaches as foundation.
Further, described alkali is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution, barium hydroxide water
One in solution, ammonia, triethylamine, phosphate, carbonate, hydrophosphate, borate and silicate
Or it is multiple.
Further, the mol ratio of described formaldehyde and tripolycyanamide is preferably 1.5～5.0: 1.The height of mol ratio
Synthesized resin property is had material impact, and mol ratio is the lowest, and synthesized resin substitution value is not enough,
Poor activity, after solidification, crosslink density is low, and heat resistance is poor.But mol ratio is the highest, then synthetic resin middle reaches
High from formaldehyde, and react wayward, in course of reaction, easily crosslink solidification, in the present invention, institute
The mol ratio stating formaldehyde and tripolycyanamide is preferably 1.5～5.0: 1.
Embodiment
Each amounts of components in table 1, table 2 and table 3 represents with the percentage ratio accounting for moulding compound gross weight.
According to the melamino-formaldehyde of comparative example 1～3 in the embodiment 1 shown in Tables 1 and 2～6 and table 3
The formula of moulding compound, is prepared as follows melamine formaldehyde molding compound:
(1) mediate: weigh boron modification melamine resin, reinforcing fiber, inorganic filler, firming agent,
Accelerator, coupling agent and releasing agent, mediate 20～40 minutes at a temperature of 60～80 DEG C, mixed uniformly
Material；
(2) plasticate: the compound using double roller mill to obtain step (1) is plasticated, mill
Before machine, roll temperature is 80～110 DEG C, and rear roll temperature is 130～150 DEG C, and the time of plasticating is 10～20 minutes,
To melamine formaldehyde molding compound.
In Tables 1 and 2, the boron modification melamine resin in embodiment 1, embodiment 2 is triphenyl
The melamine resin that borate is modified, resin is mainly by the molecular composition with following structure (I)；
Boron modification melamine resin in embodiment 2 and embodiment 3 is that diphenyl-borinic acids-2-amino ethyl ester changes
The melamine resin of property, resin is mainly by the molecular composition with following structure (II)；Embodiment 5
In boron modification melamine resin be the ester modified tripolycyanamide first of the norvalyl diphenyl-borinic acids of L-
Urea formaldehyde, resin is mainly by the molecular composition with following structure (III)；Boron modification three in embodiment 6
Melamine-formaldehyde resin is the melamine resin that L-cysteinyl-diphenyl-borinic acids is ester modified, resin
Main by the molecular composition with following structure (IV):
In formula, R1′、R2′……R9' it is independently selected from H or CH2OH or following group:
And R1′、R2′……R9In ' at least one be following group:
R1″、R2″……R5" it is independently selected from H or CH2OH or following group:
Table 1
Table 2
Comparative example
The formula of the melamine formaldehyde molding compound according to the comparative example 1～3 shown in table 3, according to embodiment
1～6 identical methods prepare melamine formaldehyde molding compound, and wherein melamine resin is unmodified general
Logical melamine resin.
Table 3
The performance test data of each embodiment and comparative example is as shown in table 4 below.
Table 4
From shown in table 4 it can be seen that use melamine formaldehyde molding compound that the inventive method prepares with
Common melamine formaldehyde molding compound is compared, and has the most excellent heat resistance, dimensional stability and machinery
Performance.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every profit
The equivalents made by description of the invention content, or directly or indirectly it is used in relevant technical field,
The most in like manner it is included in the scope of patent protection of the present invention.
Claims (9)
1. a melamine formaldehyde molding compound, it is characterised in that include the component of following weight portion:
Described boron modification melamine resin is prepared by following methods:
1) formaldehyde of organoboron compound and excess is added in reactor, stir, regulate reactant liquor with alkali
PH be 8 10, be warming up to 80 120 DEG C, react 1 4h；
2) to step 1) reactant liquor of gained adds tripolycyanamide, stir and react 1 6h, obtaining boron modification
Melamine resin；
Described organoboron compound is selected from triphenyl borine acid esters, diphenyl-borinic acids 2 amino ethyl ester, L norvalyl
One or more in base diphenyl-borinic acids ester, L cysteinyl-diphenyl-borinic acids ester；
The consumption of described organoboron compound is 5% the 40% of tripolycyanamide quality, described formaldehyde and melamine
The mol ratio of amine is 1.5 5.0: 1.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described formaldehyde is
The formalin of mass concentration 30% 50%.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described enhancing fibre
Dimension is selected from carbon fiber, basalt fibre, polyester fiber, alumina fibre, wood powder, paper powder, bamboo powder and glass
One or more in glass fiber.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described inorganic fill out
One or more in calcium carbonate, Pulvis Talci, mica powder, wollastonite powder and flake asbestos of material.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described firming agent
One or more in hexamethylenamine, triethylamine and p-methyl benzenesulfonic acid.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described accelerator
One or more in calcium oxide, magnesium oxide, calcium hydroxide and magnesium hydroxide.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described coupling agent
Selected from titanate coupling agent, aluminate coupling agent, silane coupler, boric acid ester coupler and phosphate ester coupling
One or more in agent.
Melamine formaldehyde molding compound the most according to claim 1, it is characterised in that: described releasing agent
One or more in stearic acid, calcium stearate, magnesium stearate and aluminium stearate.
9. a preparation method for the melamine formaldehyde molding compound as described in claim 1 to 8 any one,
It is characterized in that, comprise the following steps:
(1) mediate: weigh described boron modification melamine resin, reinforcing fiber, inorganic filler,
Firming agent, accelerator, coupling agent and releasing agent, mediate 20～40 minutes at a temperature of 60～80 DEG C, obtains all
Even compound；
(2) plasticate: the compound using double roller mill to obtain step (1) is plasticated, mill
Before machine, roll temperature is 80～110 DEG C, and rear roll temperature is 130～150 DEG C, and the time of plasticating is 10～20 minutes,
To melamine formaldehyde molding compound.
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| CN1323113C (en) * | 2004-12-17 | 2007-06-27 | 上海欧亚合成材料有限公司 | High-performance melamine-phenol-formaldehyde molding compound |
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| CN1323113C (en) * | 2004-12-17 | 2007-06-27 | 上海欧亚合成材料有限公司 | High-performance melamine-phenol-formaldehyde molding compound |
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