(3) summary of the invention
Although the technology of relevant phenol formaldehyde foam modification is many, a lot of technology have all been sacrificed the fire resistance of phenol formaldehyde foam in toughness reinforcing.The present invention proposes a kind of special chemical method for toughening that adopts just at this difficult problem, and preferred marvellous auxiliary curing agent is special to obtain a kind of structure, not only toughness reinforcing but also non-combustible closed pore toughening metlbond foam plastics.
The phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: (1.30~2.50), catalyzer are the binary complex body, and modified additive is silicon intermediate, ester compound, ammoniac compounds.Its component and content by weight are (is 100 parts with phenol):
Formaldehyde 100~220, catalyzer 0.8~8, silicon intermediate 2~10, ammoniac compounds 2~10, ester compound 2~10; Foaming formulation is a resin 100, tensio-active agent 1~5, whipping agent 2~12, auxiliary curing agent 0.5-5, solidifying agent 4~15.
Said catalyzer is selected from the binary complex body, can be at least a in highly basic and the metal oxide, and wherein highly basic is 0.5~5, and metal oxide is 0.3~3.
Tensio-active agent is selected from DC-190, DC-193, L-530, L-5310, L-158, tween 80, polysorbate40 or polysorbate60 etc.
Whipping agent is selected from Skellysolve A, iso-pentane, sherwood oil or alkane etc.
Auxiliary curing agent is selected from borax, powdered silica, aluminium hydroxide or cupric oxide etc.
Solidifying agent can adopt organic acid, is selected from phenol sulfonic acid, tosic acid, xylene monosulfonic acid, oxalic acid or acetate etc.
The said closed pore toughening metlbond foam of the present invention plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 50~85 ℃ of reaction 40~60min, at 90~100 ℃ of reaction 100~150min;
2, add ammoniac compounds and continue reaction, temperature is 90-102 ℃, and the reaction times is 5-15min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, add solidifying agent and heat 50~100 ℃, 10~120min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
The present invention has adopted special chemical method for toughening and marvellous auxiliary curing agent, add three class modified additives respectively, adopt alkane to make whipping agent, no global greenhouse effect coefficient obtains the special closed pore toughening metlbond foam plastics of structure, has solved the problem that hinders the phenol formaldehyde foam development, final phenol formaldehyde foam rate of closed hole is greatly less than 85%, fragility is less than 25%, and thermal conductivity helps applying of phenolic foamed plastics less than 0.025W/mk.
(4) embodiment
Following examples will the present invention is further illustrated.
Embodiment 1: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 2, its component and content by weight are (is 100 parts with phenol): formaldehyde 170, catalyzer adopts highly basic 1, metal oxide 1, silicon intermediate 6, ammoniac compounds 5, ester compound 3; Foaming formulation is a resin 100, and tensio-active agent is selected L-158 3.5 for use, and whipping agent is selected from alkane 8, and solidifying agent is selected from tosic acid 10.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 60 ℃ of reaction 50min, at 95 ℃ of reaction 150min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin:
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, and the adding solidifying agent (identical or different with auxiliary curing agent, there is not auxiliary curing agent in the above-mentioned component, term name is unified in PLSCONFM! ) stir 100s, heat 75 ℃, 80min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 2: the phenol and the formaldehyde mole ratio of its synthesis modification resol of closed pore toughening metlbond foam plastics are 1: 1.5, its component and content by weight are (is 100 parts with phenol): formaldehyde 125, catalyzer adopts highly basic 3, metal oxide 0.5, silicon intermediate 8, ammoniac compounds 2, ester compound 6; Foaming formulation is a resin 100, and tensio-active agent selects 2 for use, and whipping agent is selected from sherwood oil 4, and solidifying agent is selected from phenol sulfonic acid 15.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 45min, at 90 ℃ of reaction 120min;
2, add ammoniac compounds and continue reaction, temperature is 100 ℃, and the reaction times is 5min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, and the adding solidifying agent (identical or different with auxiliary curing agent, there is not auxiliary curing agent in the above-mentioned component, term name is unified in PLSCONFM! ) stir 150s, heat 60 ℃, 50min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 3: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 1.3, its component and content by weight are (is 100 parts with phenol): formaldehyde 110, catalyzer adopts highly basic 0.5, metal oxide 3, silicon intermediate 4, ammoniac compounds 10, ester compound 2; Foaming formulation is a resin 100, and tensio-active agent is selected " tween 80 " 4 for use, and whipping agent is selected from alkane 12, and solidifying agent is selected from tosic acid 8.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 60 ℃ of reaction 60min, at 100 ℃ of reaction 130min;
2, add ammoniac compounds and continue reaction, temperature is 100 ℃, and the reaction times is 5min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, and the adding solidifying agent (identical or different with auxiliary curing agent, there is not auxiliary curing agent in the above-mentioned component, term name is unified in PLSCONFM! ) stir 80s, heat 80 ℃, 100min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 4: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 1.8, its component and content by weight are (is 100 parts with phenol): formaldehyde 158, catalyzer adopts highly basic 5, metal oxide 0.3, silicon intermediate 10, ammoniac compounds 6, ester compound 10; Foaming formulation is a resin 100, and tensio-active agent is selected " DC-193 " 1 for use, and whipping agent is selected from alkane 10, and solidifying agent is selected from tosic acid 4.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 85 ℃ of reaction 50min, at 90 ℃ of reaction 100min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, add solidifying agent and stir 120s, heat 100 ℃, 120min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 5: the phenol and the formaldehyde mole ratio of its synthesis modification resol of closed pore toughening metlbond foam plastics are 1: 2.3, its component and content by weight are (is 100 parts with phenol): formaldehyde 200, catalyzer adopts highly basic 4, metal oxide 2, silicon intermediate 2, ammoniac compounds 8, ester compound 8: foaming formulation is a resin 100, tensio-active agent is selected " L-158 " 5 for use, and whipping agent is selected from alkane 2, and solidifying agent is selected from tosic acid 12.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 40min, at 95 ℃ of reaction 110min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, add solidifying agent and stir 30s, heat 50 ℃, 30min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 6: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 2.5, its component and content by weight are (is 100 parts with phenol): formaldehyde 220, catalyzer adopts highly basic 3.5, metal oxide 1.5, silicon intermediate 5, ammoniac compounds 4, ester compound 5; Foaming formulation is a resin 100, and tensio-active agent is selected " polysorbate60 " 3 for use, and whipping agent is selected from alkane 6, and solidifying agent is selected from tosic acid 6.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 55min, at 95 ℃ of reaction 125min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 30min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent, auxiliary curing agent are mixed, add solidifying agent and stir 50s, heat 90 ℃, 10min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.