CN100447216C - Flame-proof non-formaldehyde wood adhesive and preparation method thereof - Google Patents
Flame-proof non-formaldehyde wood adhesive and preparation method thereof Download PDFInfo
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- CN100447216C CN100447216C CNB200610021957XA CN200610021957A CN100447216C CN 100447216 C CN100447216 C CN 100447216C CN B200610021957X A CNB200610021957X A CN B200610021957XA CN 200610021957 A CN200610021957 A CN 200610021957A CN 100447216 C CN100447216 C CN 100447216C
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Abstract
The present invention discloses one kind of fire retarding no-formaldehyde wood adhesive, which contains polyvinyl alcohol 15-35 weight portions, P and B containing inorganic acid 4-8 weight portions, organic amine containing polyamino group 4-8 weight portions, preservative 1-5 weight portions, stuffing 0-10 weight portions and water 70-125 weight portions; and has pH value of 5.0-7.0. The present invention also discloses the preparation process of the wood adhesive, and the preparation process is simple and easy to control. The wood adhesive has fire retarding components P and B grafted to polyvinyl alcohol, so that it has no formaldehyde released to harm environment and human body.
Description
Technical field
The invention belongs to wood adhesive and preparation method thereof technical field, be specifically related to a kind of flame-proof non-formaldehyde wood adhesive and preparation method thereof.
Background technology
At present, be used for the tackiness agent of timber, three-aldehyde glue i.e. " urea-formaldehyde glue, phenolic glue, trimeric cyanamide formal " glue accounts for more than 95%.Because it is raw material that three-aldehyde glue adopts poisonous and harmful elements such as formaldehyde, phenol, benzene aborning mostly, thereby make in the finished product of its three formaldehyde wood adhesive and have the higher free formaldehyde of content, these formaldehyde can discharge in the production of shaving board, glued board etc. and use gradually, environment and human body are caused very big harm, found unambiguous evidence as domestic and international scientist, confirm that formaldehyde can be by influencing the DNA expression regulation, influencing apoptosis, biomacromolecule (as DNA, protein) is caused mechanism such as oxidative damage, cause the histocyte canceration.For this reason, each state all formulated strict relatively artificial board formaldehyde discharge limit the quantity of and the city air in the permissible value of formaldehyde amount.Though China has also formulated strict " burst size of methanal is limited the quantity of in indoor decorating material-wood-based plate and the goods thereof " mandatory national standard (GB18580-2001) in calendar year 2001, but this standard does not provide because of suitable formaldehyde-free wood adhesive is arranged, make it the people's will part in commission occur much being not so good as, cause burst size of methanal to exceed standard even the wood-based plate of severe overweight is still sold on market, formaldehyde content exceeds standard in the interior decoration air, and the example that is detrimental to health is of common occurrence.Therefore eliminate gradually " three-aldehyde glue ", developing new nontoxic environment-friendly type wood adhesive is an instant thing.
The present various countries of flame retardant type shaving board still are in the laboratory study stage, and the methods of adding fire retardant that adopt reach acquisition more, the fire retardant that is adopted has boric acid, aluminium hydroxide, zinc borate, diammonium hydrogen phosphate, polyphosphoric acid amine etc., and concrete addition means adopts pickling process (Chinese patent CN1053386A) more.Produce not only energy consumption height of fire-resistant-chipboard in this way, need special equipment, technical fee is big, and wood shavings can produce expansion in steeping process, thereby influences the intensity of sheet material.In addition, the fire-resistant-chipboard that this method is produced is placed in the fire retardant in the plate is run off gradually, can reduce or lose its flame retardant resistance on the one hand, also will pollute environment on the other hand.Except flooding fire-retardant method, carry out the two kinds of main method that also have of fire-retardant finish in the making sheet process: a kind of is the fire retardant spray to be added in carry out fire-retardant finish on the wood shavings, the time that spray adds fire retardant be selected in spray glue before, spray into simultaneously with glue or spray glue after all can.This method has certain limitation to the fire retardant applied amount, because fire retardant and tackiness agent all are water miscible, when the water content of tackiness agent is big, the applied amount of fire retardant is big, then easily from the shaving board course of processing, separate out, run off, form waste, contaminate environment on the other hand on the one hand.Another kind is that fire retardant is added in the tackiness agent in the mode of mechanically mixing earlier, and then adds to (Xiao Xiaobing, fire-resistant-chipboard production technology, the woodworking machine third phase in 2000) on the wood shavings.Though the fire retardant that this method applies can be evenly distributed on the wood shavings, resistance leachability is good, and 1. water miscible fire retardant can be brought large quantity of moisture into, causes that the shaving board water ratio increases after the applying glue, makes troubles to hot pressing; 2. be subjected to the influence of fire retardant pH value, can be to the detrimentally affect that is solidified with of tackiness agent, thus influence the physical and mechanical property of shaving board; 3. the fire retardant addition is limited, and flame retardant effect is not satisfactory.
Summary of the invention
The objective of the invention is problem, a kind of flame-proof non-formaldehyde wood adhesive is provided at the prior art existence.
Another object of the present invention provides a kind of method for preparing above-mentioned flame-proof non-formaldehyde wood adhesive.
A kind of flame-proof non-formaldehyde wood adhesive provided by the invention, it is characterized in that this tackiness agent by weight, wherein contain: 15～35 parts of polyvinyl alcohol, 4～8 parts of phosphorous or boron mineral acids, 4～8 parts of organic amines that contain the polyamines base, 1～5 part of sanitas, 70～125 parts in water, and its pH value is 5.0～7.0.
For reducing cost, this tackiness agent wherein also contains 0～10 part of filler by weight.This filler is selected from wilkinite, diatomite, any in talcum powder, glass powder, the sawdust.
Phosphorous or boron mineral acid is selected from phosphoric acid, tetra-sodium or boric acid in the above-mentioned tackiness agent; The organic amine that contains the polyamines base is selected from urea, biuret or Dyhard RU 100; Sanitas is selected from least a in boric acid, borax, P-hydroxybenzoic acid pentyl ester, the sulphite.
A kind of method for preparing flame-proof non-formaldehyde wood adhesive provided by the invention is characterized in that the processing step of this method and condition are as follows:
1) to being added with 100 parts of water and having in the container of heating, agitator, under heating condition, adds 15～35 parts of polyvinyl alcohol while stirring, dissolve fully, 70～95 ℃ of temperature controls to it;
2) under 25～95 ℃ of temperature, add 4～8 parts of phosphorous or boron mineral acid and 4～8 parts of organic amines that contain the polyamines base while stirring, it is fully dissolved;
3) obtaining mixture is moved to baking oven, dry by the fire 3～5 hours down to colloidal 60～90 ℃ of temperature;
4) in the container of heating stirrer, under the stirring that heats up, above step is obtained the colloid thing be dissolved in again in 85～110 parts of water, 70～95 ℃ of temperature controls;
5) at ambient temperature, add acidity regulator while stirring, it is fully dissolved, the pH value of solution is adjusted to 5.0～7.0;
6) at ambient temperature, add 1～5 portion of sanitas while stirring, it is fully dissolved.
7) at ambient temperature, add 0～10 part of filler while stirring, it is evenly got final product.
The step 2 of this method) the phosphorous or boron mineral acid described in is selected from phosphoric acid, tetra-sodium or boric acid, and the organic amine that contains the polyamines base is selected from urea or Dyhard RU 100; Acidity regulator described in the step 5) is selected from least a in urea, Dyhard RU 100, ammonia chloride, diammonium hydrogen phosphate, oxysuccinic acid, the tartrate; Sanitas described in the step 6) is selected from least a in boric acid, borax, P-hydroxybenzoic acid pentyl ester, the sulphite; Filler described in the step 7) is selected from wilkinite, diatomite, any in talcum powder, glass powder, the sawdust.
What deserves to be explained is step 2 in addition) in polyvinyl alcohol preferably to adopt the polymerization degree be 1700 and above polyvinyl alcohol.
Churning time in this method in the step 1) is 30～50 minutes, step 2) churning time in is 10～20 minutes, churning time in the step 4) is 30～50 minutes, churning time in the step 5) is 5～10 minutes, churning time in the step 6) is 5～10 minutes, and the churning time in the step 7) is 5～10 minutes.
Compared with the prior art the present invention has the following advantages and positively effect:
1, do not add the aldehydes component owing in the tackiness agent provided by the invention, thereby formaldehydeless release in production and use, the injury of formaldehyde release avoided to environment and human body.
2, because flame-retardant composition phosphorus, boron in the tackiness agent provided by the invention are to be connected on the polyvinyl alcohol by reacting phase, thereby avoided dipping, spray to add or the mechanically mixing addition manner adds the fire retardant that fire retardant brings and runs off, pollutes, addition is limited, flame retardant effect is poor, to the curing of tackiness agent and as a series of problems such as influence of the physical and mechanical property of adherent shaving board own.
3, directly contain flame-retardant composition owing in the tackiness agent provided by the invention, thus the energy consumption height of also having avoided pickling process to bring, needing special equipment, technical fee is big, and wood shavings can produce expansion in steeping process, thereby influences the problems such as intensity of sheet material.
4, tackiness agent binding property provided by the invention is good, the flame retardant resistance height, and with its adherent such as shaving board good combination property, can be not the depositing in the process of wet environment, reduce or lose its flame retardant resistance.
5, preparation method provided by the invention is simple, and technical maturity is easy to control.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the present invention is further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection domain of the present invention.
Embodiment 1
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 15 parts of trades mark while stirring and be 1799 polyvinyl alcohol, and be warming up to 70 ℃, stirred 45 minutes, it is dissolved fully; Under 25 ℃ of temperature, add 4 parts of phosphoric acid and 4 parts of urea while stirring, keep stirring 12 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 5 hours down to colloidal 60 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 85 parts of water again, and 70 ℃ of temperature controls keep stirring 45 minutes; At ambient temperature, add urea while stirring, keep stirring 6 minutes, make the pH value of solution be adjusted to 6.5, add 1 part of boric acid then while stirring, keep stirring 10 minutes, it is fully dissolved, add 10 parts of wilkinites at last while stirring, it is evenly got final product.
Embodiment 2
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 20 parts of trades mark while stirring and be 1799 polyvinyl alcohol, and be warming up to 80 ℃, stirred 50 minutes, it is dissolved fully; Under 45 ℃ of temperature, add 5 parts of tetra-sodiums and 5 parts of Dyhard RU 100s while stirring, keep stirring 10 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 4 hours down to colloidal 70 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 90 parts of water again, and 80 ℃ of temperature controls keep stirring 40 minutes; At ambient temperature, add Dyhard RU 100 while stirring, keep stirring 5 minutes, make the pH value of solution be adjusted to 7.0, add 1 part of borax then while stirring, keep stirring 8 minutes, it is fully dissolved, add 10 parts of diatomite at last while stirring, keep stirring to get final product in 7 minutes.
Embodiment 3
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 35 parts of trades mark while stirring and be 1788 polyvinyl alcohol, and be warming up to 95 ℃, stirred 45 minutes, it is dissolved fully; Under 95 ℃ of temperature, add 8 parts of boric acid and 8 parts of urea while stirring, keep stirring 20 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 3 hours down to colloidal 90 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 110 parts of water again, and 95 ℃ of temperature controls keep stirring 30 minutes; At ambient temperature, add tartrate while stirring, keep stirring 8 minutes, make the pH value of solution be adjusted to 5.0, add 5 parts of P-hydroxybenzoic acid pentyl esters then while stirring, keep stirring 7 minutes, it is fully dissolved get final product.
Embodiment 4
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 25 parts of trades mark while stirring and be 1799 polyvinyl alcohol, and be warming up to 90 ℃, stirred 30 minutes, it is dissolved fully; Under 65 ℃ of temperature, add 6 parts of phosphoric acid and 6 parts of urea while stirring, keep stirring 18 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 3.5 hours down to colloidal 80 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 95 parts of water again, and 85 ℃ of temperature controls keep stirring 35 minutes; At ambient temperature, add diammonium hydrogen phosphate while stirring, keep stirring 10 minutes, make the pH value of solution be adjusted to 6.0, add 1 part of boric acid and 2 parts of boraxs then while stirring, keep stirring 6 minutes, it is fully dissolved, add 5 parts of talcum powder at last while stirring, keep stirring to get final product in 5 minutes.
Embodiment 5
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 28 parts of trades mark while stirring and be 1799 polyvinyl alcohol, and be warming up to 90 ℃, stirred 38 minutes, it is dissolved fully; Under 90 ℃ of temperature, add 8 parts of phosphoric acid and 8 parts of biurets while stirring, keep stirring 14 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 3.5 hours down to colloidal 85 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 103 parts of water again, and 90 ℃ of temperature controls keep stirring 36 minutes; At ambient temperature, add urea while stirring, keep stirring 8 minutes, make the pH value of solution be adjusted to 5.3, add 3 parts of boraxs then while stirring, keep stirring 6 minutes, it is fully dissolved, add 7 parts of sawdusts at last while stirring, keep stirring to get final product in 8 minutes.
Embodiment 6
100 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 30 parts of trades mark while stirring and be 1788 polyvinyl alcohol, and be warming up to 90 ℃, stirred 40 minutes, it is dissolved fully; Under 85 ℃ of temperature, add 7 parts of boric acid and 7 parts of Dyhard RU 100s while stirring, keep stirring 20 minutes, it is fully dissolved; Obtaining mixture is moved to baking oven, dry by the fire 3 hours down to colloidal 90 ℃ of temperature, this colloidal mixture contains the moisture about 15%; Obtaining colloid thing under the stirring that heats up, is dissolved in 105 parts of water again, and 90 ℃ of temperature controls keep stirring 30 minutes; At ambient temperature, add oxysuccinic acid while stirring, keep stirring 7 minutes, make the pH value of solution be adjusted to 5.5, add 4 parts of S-WATs then while stirring, keep stirring 5 minutes, it is fully dissolved, add 2 parts of glass powder at last while stirring, keep stirring to get final product in 10 minutes.
Comparative Examples
95 parts of water are put into the container that has heating, agitator, in heating, stir speed (S.S.) is under 200 rev/mins of conditions, add 25 parts of trades mark while stirring and be 1799 polyvinyl alcohol, and be warming up to 90 ℃, stirred 30 minutes, it is dissolved fully; At ambient temperature, add diammonium hydrogen phosphate while stirring, keep stirring 10 minutes, make the pH value of solution be adjusted to 6.0, add 1 part of boric acid and 2 parts of boraxs then while stirring, keep stirring 6 minutes, it is fully dissolved, add 5 parts of talcum powder at last while stirring, keep stirring to get final product in 5 minutes.
Method with flame-proof non-formaldehyde wood adhesive provided by the invention is: at room temperature the tackiness agent of 10～-25 weight parts and 2～5 parts of isocyanate curing agent PAPI (polymethylene multi-phenenyl isocyanate) or MDI ('-diphenylmethane diisocyanate) are mixed, and use in half hour.
For investigating the application performance of flame-proof non-formaldehyde wood adhesive of the present invention, the present invention is used to produce the wooden shavings plate with each embodiment and tackiness agent that Comparative Examples obtains, its mask-making technology following (can change resin added and hot pressing template): earlier the tackiness agent of 15 weight parts and the solidifying agent PAPI of 3 weight parts are mixed according to different needs, be that 82 wood chip fully stirs in agitator with weight part then, make tackiness agent be dispersed in the wood chip uniformly, then it is placed in the template, put into thermocompressor, 60 ℃ of hot pressing temperatures, pressure 10 kg/cm, hot pressing was carried out hot pressing under 20 minutes, and hot pressing gained sample made batten according to GB 4899,4901,4902,4903-85 has tested its density, expansion rate of water absorption, internal bond strength, MOR and tested its oxygen index according to GB/T 2406-93, it the results are shown in following table:
| Embodiment | Density (g/cm 3) | MOR (N/mm 2) | Thickness swelling rate (%) | Internal bond strength (N/mm 2) | Oxygen index (%) |
| 1 | 0.76 | 17.2 | 8.6 | 0.44 | 34.1 |
| 2 | 0.76 | 17.5 | 8.6 | 0.44 | 36.3 |
| 3 | 0.76 | 17.8 | 8.7 | 0.46 | 35.0 |
| 4 | 0.78 | 17.9 | 9.2 | 0.41 | 41.5 |
| 5 | 0.78 | 17.5 | 9.0 | 0.43 | 39.7 |
| 6 | 0.77 | 17.5 | 8.9 | 0.44 | 37.4 |
| Comparative Examples | 0.74 | 18.2 | 8.4 | 0.47 | 26.4 |
Claims (8)
1, a kind of flame-proof non-formaldehyde wood adhesive, it is characterized in that this tackiness agent by weight, wherein contain: the polymerization degree is 15～35 parts of polyvinyl alcohol more than 1700,4～8 parts of phosphorous or boron mineral acids, 4～8 parts of organic amines that contain the polyamines base, 1～5 part of sanitas, 70～125 parts in water, and its pH value is 5.0～7.0, and the organic amine that contains the polyamines base is selected from urea, biuret or Dyhard RU 100.
2, flame-proof non-formaldehyde wood adhesive according to claim 1 is characterized in that this tackiness agent by weight, wherein also contains 0～10 part of filler.
3, flame-proof non-formaldehyde wood adhesive according to claim 2 is characterized in that wherein filler is selected from wilkinite, diatomite, any in talcum powder, glass powder, the sawdust.
4,, it is characterized in that wherein phosphorous or the boron mineral acid is selected from phosphoric acid, tetra-sodium or boric acid according to claim 1 or 2 or 3 described flame-proof non-formaldehyde wood adhesives.
5,, it is characterized in that sanitas wherein is selected from least a in boric acid, borax, P-hydroxybenzoic acid pentyl ester, the sulphite according to claim 1 or 2 or 3 described flame-proof non-formaldehyde wood adhesives.
6, a kind of method for preparing the described flame-proof non-formaldehyde wood adhesive of claim 1 is characterized in that the processing step of this method and condition are as follows:
1) to being added with 100 parts of water and having in the container of heating, agitator, under heating condition, add 15～35 parts of polymerization degree while stirring and be the polyvinyl alcohol more than 1700, dissolve 70～95 ℃ of temperature controls fully to it;
2) under 25～95 ℃ of temperature, add 4～8 parts of phosphorous or boron mineral acid and 4～8 parts of organic amines that contain the polyamines base while stirring, it is fully dissolved, the organic amine that wherein contains the polyamines base is selected from urea, biuret or Dyhard RU 100;
3) obtaining mixture is moved to baking oven, dry by the fire 3～5 hours down to colloidal 60～90 ℃ of temperature;
4) in the container of heating stirrer, under the stirring that heats up, above step is obtained the colloid thing be dissolved in again in 85～110 parts of water, 70～95 ℃ of temperature controls;
5) at ambient temperature, add acidity regulator while stirring, it is fully dissolved, the pH value of solution is adjusted to 5.0～7.0;
6) at ambient temperature, add 1～5 portion of sanitas while stirring, it is fully dissolved
7) at ambient temperature, add 0～10 part of filler while stirring, it is evenly got final product.
7, the method for preparing flame-proof non-formaldehyde wood adhesive according to claim 6 is characterized in that the step 2 of this method) described in phosphorous or boron mineral acid be selected from phosphoric acid, tetra-sodium or boric acid; Acidity regulator described in the step 5) is selected from least a in urea, Dyhard RU 100, ammonia chloride, diammonium hydrogen phosphate, oxysuccinic acid, the tartrate; Sanitas described in the step 6) is selected from least a in boric acid, borax, P-hydroxybenzoic acid pentyl ester, the sulphite; Filler described in the step 7) is selected from wilkinite, diatomite, any in talcum powder, glass powder, the sawdust.
8, according to claim 6 or the 7 described methods that prepare flame-proof non-formaldehyde wood adhesive, it is characterized in that the churning time in the step 1) is 30～50 minutes in this method, step 2) churning time in is 10～20 minutes, churning time in the step 4) is 30～50 minutes, churning time in the step 5) is 5～10 minutes, churning time in the step 6) is 5～10 minutes, and the churning time in the step 7) is 5～10 minutes.
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| CNB200610021957XA CN100447216C (en) | 2006-09-28 | 2006-09-28 | Flame-proof non-formaldehyde wood adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104403603A (en) * | 2014-10-22 | 2015-03-11 | 上海大学 | Flame-retardant cross-linked polyvinyl alcohol binder and preparation method thereof |
| CN105368347A (en) * | 2015-11-23 | 2016-03-02 | 苏州盖德精细材料有限公司 | Polyvinyl alcohol instant glue and preparation method thereof |
| CN105273665A (en) * | 2015-11-27 | 2016-01-27 | 济南昊泽环保科技有限公司 | Waterborne adhesive and preparation method thereof |
| CN111019563A (en) * | 2019-12-26 | 2020-04-17 | 厦门市启亚星纸制品有限公司 | Glue-coated and conveniently-torn notebook for notebook and notebook manufacturing process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500848A (en) * | 2002-11-19 | 2004-06-02 | 白以晟 | Aldehyde free building adhesive and preparing method thereof |
| CN1712484A (en) * | 2004-06-24 | 2005-12-28 | 湖南省浏阳市三星化工实业有限公司 | Binder for production of non-formaldehyde artificial boards |
| CN1730591A (en) * | 2005-08-11 | 2006-02-08 | 忻健存 | Novel environment protective adhesives free of formaldehyde and its manufacturing process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1500848A (en) * | 2002-11-19 | 2004-06-02 | 白以晟 | Aldehyde free building adhesive and preparing method thereof |
| CN1712484A (en) * | 2004-06-24 | 2005-12-28 | 湖南省浏阳市三星化工实业有限公司 | Binder for production of non-formaldehyde artificial boards |
| CN1730591A (en) * | 2005-08-11 | 2006-02-08 | 忻健存 | Novel environment protective adhesives free of formaldehyde and its manufacturing process |
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