阅读说明：本技术 利用含铬革屑制作颗粒板的方法 (Utilize the method for chrome leather scrap production particle board ) 是由 段宝荣 王全杰 仇同济 王琦研 于 2019-09-11 设计创作，主要内容包括：本发明涉及一种利用含铬革屑制作颗粒板的方法,蓝皮革屑经过处理后与胶、氮磷系阻燃剂、增韧剂、增韧协效剂、阻燃性合成加脂剂、抑制水膨胀剂以及水性透明防水剂混合均匀,放入模具,在平板硫化机内加热加压,养护,最终得到外表均匀的板材作颗粒板,所得颗粒板在阻燃、耐水膨胀率、耐磨耗性等方面具有良好的性能。(The present invention relates to a kind of methods using chrome leather scrap production particle board, blue leather bits are uniformly mixed with glue, nitrogen phosphorus flame retardant, toughener, toughening synergist, anti-flammability synthetic fat liquor, inhibition water swelling agent and aqueous transparent waterproofing agent after treatment, it is put into mold, pressurization is heated in vulcanizing press, maintenance, finally obtain the uniform plate of appearance and make particle board, gained particle board fire-retardant, water-fast expansion rate, in terms of it is with good performance.)

1. utilizing the method for chrome leather scrap production particle board, it is characterised in that follow the steps below:

(1), blue leather bits are added to the water, adjust pH to 4 ~ 4.5 after addition oxalic acid stirring, trisodium citrate dihydrate is added and stirs It mixes, dries；

(2), blue leather bits, the glue, nitrogen phosphorus flame retardant, toughener, toughening synergist, anti-flammability that will be dried obtained by step (1) Synthetic fat liquor inhibits water swelling agent, substance A, aqueous transparent waterproofing agent to be uniformly mixed, and is put into mold, heats in vulcanizer Gained plate is placed into maintenance in climatic chamber and obtains particle board by pressurization；

Toughener is any one of nitrile rubber, polyvinyl butyral；

Toughening synergist be vinyl sodium benzosulfonate, malonic acid ring (Asia) isopropyl ester, 3,4- dimethylaniline it is any one Kind；

Substance A is any one of n-butylbenzoic acid, trimethylolpropane and cinnamamide.

2. as described in claim 1 using chrome leather scrap production particle board method, it is characterised in that according to the following steps into Row:

(1), blue leather bits 60g, oxalic acid 1 ~ 3g and 90g water are uniformly mixed, 1 ~ 2h are stirred at 35 ~ 40 DEG C, then adjust pH to 4 ~ 4.5,0.4 ~ 0.7g of trisodium citrate dihydrate is added, stirs 30 ~ 60min, gained indigo plant skin chromium is considered to be worth doing and is dried；

(2), all blue leather bits of step (1), 13.2 ~ 21.1g of glue, 2 ~ 8g of nitrogen phosphorus flame retardant, 1 ~ 3g of toughener, toughening are assisted It imitates 0.2 ~ 0.5g of agent, 5 ~ 7g of anti-flammability synthetic fat liquor, inhibit 0.9 ~ 2.1g of water swelling agent, 0.7 ~ 2.5g of substance A, aqueous transparent Waterproofing agent WP01 is uniformly mixed for 0.2 ~ 0.6g, places 30 ~ 60min at normal temperature, is put on 4mm thickness mold, vulcanizing press Pressure is 10 ~ 12Mpa, and temperature is 90 ~ 100 DEG C, pressurization is heated in vulcanizing press, process time is 30 ~ 60min, by institute It obtains plate and is placed into 48h in climatic chamber, controlled at 25 DEG C, humidity 65% finally obtains the uniform plate of appearance Make leather particles plate.

3. utilizing the method for chrome leather scrap production particle board as claimed in claim 1 or 2, it is characterised in that inhibit water swelling agent Preparation method: hydroxyl dimethyl silicone polymer 15g, 10 ~ 12g of maleic anhydride are stirred to react 1 ~ 2h at 60 ~ 70 DEG C, then plus Enter 2.4 ~ 3.6g of N- 1 ~ 4g of methyl alkyl amine and 2,5-furandicarboxylic acid, stirs 20 ~ 30min at 50 ~ 80 DEG C, it is swollen to obtain the inhibition water Swollen dose.

4. utilizing the method for chrome leather scrap production particle board as claimed in claim 1 or 2, it is characterised in that the glue is poly- Urethane glue 700w or all-purpose adhesive 899.

5. utilizing the method for chrome leather scrap production particle board as claimed in claim 1 or 2, it is characterised in that the inhibition water The preparation method of swelling agent: hydroxyl dimethyl silicone polymer 15g, 10 ~ 12g of maleic anhydride are stirred to react 1 at 60 ~ 70 DEG C ~ 2h adds 2.4 ~ 3.6g of N- 1 ~ 4g of methyl alkyl amine and 2,5-furandicarboxylic acid, stirs 20 ~ 30min at 50 ~ 80 DEG C, must be somebody's turn to do Inhibit water swelling agent.

6. utilizing the method for chrome leather scrap production particle board as claimed in claim 1 or 2, it is characterised in that the nitrogen phosphorus system The preparation method of fire retardant is that dimethylphosphite 50g is added in reaction vessel, adds 0.6~2.2g of sodium methoxide and rises For temperature to 75~80 DEG C, all after dissolution, 55~85g acrylamide is added in sodium methoxide, cools to 40~50 DEG C, is added to methylbenzene 0.4 ~ 0.7g of 3.2 ~ 6.8g of sulfonic acid chloride and dodecanedioic acid, insulated and stirred react 1~2h and obtain intermediate；It is added most into intermediate PH 6.5 is adjusted with 30% NaOH afterwards, obtains nitrogen phosphorus flame retardant.

7. utilizing the method for chrome leather scrap production particle board as claimed in claim 1 or 2, it is characterised in that the anti-flammability The preparation method of synthetic fat liquor is that sulfonic chloride 15g, 10 ~ 12g of palm oil, 4 ~ 8g of neat's foot oil are warming up to 40 ~ 50 DEG C, 15 ~ 18g of maleic anhydride is added, is warming up to 80 ~ 120 DEG C, reacts 2 ~ 3h, adds 1 ~ 4g of tetrakis hydroxymetyl phosphonium sulfuric, in 50 ~ It is stirred to react 2 ~ 4h at 70 DEG C, adds 0.01 ~ 0.04g of 0.02 ~ 0.03g of preservative and antioxidant, is arrived with sodium carbonate neutralization PH is 7 ~ 7.5, obtains the anti-flammability synthetic fat liquor.

8. utilizing the method for chrome leather scrap production particle board as claimed in claim 7, it is characterised in that the preservative is anti- Rotten agent or preservative PCP30.

9. 7 method using chrome leather scrap production particle board as described in right, it is characterised in that the antioxidant is two fourths Base hydroxy-methylbenzene or tert-butyl hydroquinone.

Technical field

The present invention relates to a kind of using as the method for the chrome leather scrap of tanned wastes production particle board.

Background technique

China is the first in the world leather big producer, and 9 Yi ㎡ of leather total output accounts for about a quarter in the world.It is so high Leather output create annual 1300000000000 yuan of the output value and 88,900,000,000 dollars of export amount.The environment band in China is also given simultaneously The pollution for having carried out flood tide, other than contaminated wastewater, the pollution of solid waste also has become Social Ecology problem.Whole world system About 5,000,000 tons of waste total amount of leather, wherein up to 1,400,000 tons (bits of leather containing chrome blue) of China.The bits of leather containing chrome blue belong to danger Waste is forbidden filling and be burned, it is considered to be most intractable solid waste is used to boil the industry of power low-adhesive mostly Gelatin or production regenerated leather or artificial leather flocking, but this kind of product market capacity is limited, economic benefit is meagre.Therefore in recent years The innoxious process for treating of solid leather wastes, especially leather containing chrome blue bits becomes research hotspot.

The processing method of the bits of leather containing chrome blue is divided into physical treatment mode and chemical treatments, chemical treatments at present It is current main processing ways, main includes production gelatin, albumen powder, cement blowing agent, liquid fertilizer and surfactant. The advantages of chemical treatment, is that application field is wide, and disadvantage is that secondary pollution can be generated, and needs to increase to solve secondary pollution Processing cost.Physical treatment mode is presently mainly electrostatic spinning, the advantage is that processing cost is relatively low, environmental pollution compared with Gently, but by market capacity it is limited, treating capacity is far from meet demand.

Chinese invention patent 201610298579.3, which discloses, a kind of " protein type cement blowing agent and contains the foaming agent Concrete preparation method ", chrome leather scrap is hydrolyzed to obtain shavings hydrolyzate, then carry out blistering compounding to shavings hydrolyzate It is compounded with foam stabilizing, obtains protein type foaming agent, solve the problems, such as that protein type foaming agent is at high cost.Protein type is foamed Agent is applied in cement, is prepared into foam concrete, after the drying of residue containing chromium that hydrolysis is obtained, is added to foam concrete In, a kind of novel process approach of the residue containing chromium is provided, the new formula of one kind of production foam concrete has been obtained.Both shavings is used It is prepared for the higher foaming agent of utility value and concrete, and solves shavings pollution problem.Its major defect is mainly to use Chemical treatments, not only preparation cost is high, but also can generate secondary pollution.

Chinese invention patent 201310102297.8 is related to a kind of chrome shavinge enzymolysis product in terms of producing animal feed Using the animal feed is for preventing and treating animal due to excessively feeding caused hyperglycemia；The animal feed is according to following step Suddenly it is prepared: weighing 1 parts by weight of leather protein powder, 40~60 parts by weight of corn flour, 2~4 parts by weight of flour, 2~4 weight of wheat bran Measure part, 20~35 parts by weight of dregs of beans, 1~3 parts by weight of calcium monohydrogen phosphate, 2~5 parts by weight of grease, 0.3~1 parts by weight of sodium chloride, ammonia 0.01~0.03 parts by weight of base acid, are sufficiently mixed, and dispense to get the animal feed.Chrome shavinge enzymolysis product is in production animal Application in terms of feed, which solves current chrome shavinge, cannot efficiently use in short supply with fish meal and prepare protein feed cost with it Higher problem, and under the premise of not influencing animal normal growth and development, also there is hypoglycemic effect, can effectively solve mesh The excessively high problem of preceding raising the produced fat content of animal.Since state's laws and administrative regulation forbid chrome leather scrap to enter feed neck Domain, so without economic value.

Chinese invention patent 201710312098.8 is related to a kind of preparation method of albumen based surfactants, using oxidation De- chromium is hydrolyzed in chrome shavinge by the method that calcium, ultrasonic wave, chitosan 4- (lignocaine) salicylide schiff bases combine de- chromium, then The naoh treatment that different amounts are added obtains the extremely low different peptide chain length polypeptide hydrolyzates of chromium content；By contracting Addition self-control nucleophilic catalyst, acid binding agent improve the conversion ratio of condensation during closing, and have obtained the higher albumen of product purity Based surfactants product.The surfactant has excellent emulsifying ability, foaming power, dispersion force, penetration, washing force, In There is good solubility in hot water, it is with good stability in hard water.With very wide application prospect.It belongs to chemistry Processing mode, it is at high cost, secondary pollution can be generated.

Chinese invention patent 201010202616.9 discloses a kind of method with preparing leather degreasing agents from leather-preparing leftovers, The aminosal type surfactant for being 100 by mass fraction, the neopelex 3 that mass fraction is 3~10~ 10, the sodium carbonate that the fatty alcohol polyoxyethylene ether and mass fraction that mass fraction is 3~10 are 3~10 is added separately to container In, at 35~45 DEG C, it is stirred reaction 0.5h~2h and degreasing agent is made.Degreasing agent primary raw material is from process hides inferior horn Material, is " taking from skin, be used for skin ", complies fully with recycling economy requirement.The selection of other raw and auxiliary materials is also environmentally friendly, few dirty Dye, degradable angle are set out, and the principle of synergy is coordinated in the requirement and surfactant compound that follow leather degreasing.The disadvantage is that belonging to In chemical treatments, secondary pollution can be generated.

Chinese invention patent 201610745628.3 be related to it is a kind of with waste and old scurf containing chromium production electrostatic spinning with powdered The method of villus belongs to leather technology field.This method comprises the following steps: waste and old scurf containing chromium being crushed to graininess, is done It is dry；Particulate material is dried；95-105 days are stood, sieving screening；It immerses in organic solvent, based on screening material quality, feel is added 30-40min, drain are stirred in agent；It is placed in cylinder, expects quality meter according to screening, degreasing agent operation is added, bleeding agent operation is added, Sodium bicarbonate, sodium formate and sodium citrate operation is added, dyestuff is added, color fixing agent operation is added, adds dyestuff, heating fortune Color fixing agent operation is added in row, and fatting agent operation is added, and sodium chloride operation is added, and slipping agent operation is added, out cylinder, is dehydrated, continues Drying is to get the powdered villus of the electrostatic spinning.The electrostatic spinning made from this method is fine and smooth with powdered fuzzy hand It is smooth, and can assign electrostatic spinning product good kishke feel.The disadvantage is that being limited by market capacity, consumption chrome leather scrap amount has Limit, cannot achieve the resource utilization of chrome leather scrap.

The above mode is that leather containing chrome blue considers currently used method to be worth doing, and the present invention is the money that will be considered to be worth doing for leather containing chrome blue New approach is found in sourceization processing.

Summary of the invention

The present invention provides a kind of method using chrome leather scrap production particle board, the technical problem to be solved is that: it utilizes The process hides chromium of skin containing chrome blue bits prepare a kind of particle plate for meeting requirement, and plate is made to have preferable flexibility and resistance to Mill property, and there is lower hardness and water imbibition.

Technical scheme is as follows:

Utilize the method for chrome leather scrap production particle board, it is characterised in that follow the steps below:

(1), blue leather bits are added to the water, adjust pH to 4~4.5 after addition oxalic acid stirring, two citric acid monohydrates is added Sodium simultaneously stirs, drying；

(2), by the blue leather bits dried obtained by step (1), glue, nitrogen phosphorus flame retardant, toughener, toughening synergist, resistance Combustion property synthetic fat liquor inhibits water swelling agent, substance A, aqueous transparent waterproofing agent to be uniformly mixed, and mold is put into, in vulcanizer Gained plate is placed into maintenance in climatic chamber and obtains particle board by heating pressurization；

Toughener is any one of nitrile rubber, polyvinyl butyral；

Toughening synergist be vinyl sodium benzosulfonate, malonic acid ring (Asia) isopropyl ester, 3,4- dimethylaniline it is any It is a kind of；

Substance A is any one of n-butylbenzoic acid, trimethylolpropane and cinnamamide.

Utilize the method for chrome leather scrap production particle board, the specific steps are as follows:

(1), blue leather bits 60g, oxalic acid 1~3g and 90g water are uniformly mixed, 1~2h are stirred at 35~40 DEG C, then adjust PH to 4~4.5 is saved, 0.4~0.7g of trisodium citrate dihydrate is added, stirs 30~60min, gained indigo plant skin chromium is considered to be worth doing and is dried；

(2), by all blue leather bits of step (1), 13.2~21.1g of glue, 2~8g of nitrogen phosphorus flame retardant, toughener 1~ 3g, 0.2~0.5g of toughening synergist, 5~7g of anti-flammability synthetic fat liquor, inhibition 0.9~2.1g of water swelling agent, substance A 0.7~ 2.5g, aqueous transparent waterproofing agent WP01 are uniformly mixed for 0.2~0.6g, place 30~60min at normal temperature, are put into 4mm thickness mould On tool, vulcanizing press pressure is 10~12Mpa, and temperature is 90~100 DEG C, pressurization is heated in vulcanizing press, when processing Between be 30~60min, gained plate is placed into 48h in climatic chamber, controlled at 25 DEG C, humidity 65%, finally It obtains the uniform plate of appearance and makees leather particles plate.

The preparation method of the inhibition water swelling agent: by hydroxyl dimethyl silicone polymer 15g, 10~12g of maleic anhydride It is stirred to react 1~2h at 60~70 DEG C, adds 2.4~3.6g of N- 1~4g of methyl alkyl amine and 2,5-furandicarboxylic acid, 50 20~30min is stirred at~80 DEG C, obtains the inhibition water swelling agent.

The glue is polyurethane adhesive 700w or all-purpose adhesive 899.

In the preparation method of the described inhibition water swelling agent: by hydroxyl dimethyl silicone polymer 15g, maleic anhydride 10~ 12g is stirred to react 1~2h at 60~70 DEG C, add N- 1~4g of methyl alkyl amine and 2,5-furandicarboxylic acid 2.4~ 3.6g stirs 20~30min at 50~80 DEG C, obtains the inhibition water swelling agent.

The preparation method of the nitrogen phosphorus flame retardant be dimethylphosphite 50g is added in reaction vessel, then plus Enter 0.6~2.2g of sodium methoxide and be warming up to 75~80 DEG C, after sodium methoxide all dissolves, addition 55~85g acrylamide cools to 40~50 DEG C, 3.2~6.8g of p-methyl benzene sulfonic chloride and 0.4~0.7g of dodecanedioic acid is added, insulated and stirred is reacted 1~2h and obtained Intermediate；It is added into intermediate and finally adjusts pH6.5 with 30% NaOH, obtain nitrogen phosphorus flame retardant.

The anti-flammability synthetic fat liquor preparation method be by sulfonic chloride 15g, palm oil 10~ 12g, 4~8g of neat's foot oil are warming up to 40~50 DEG C, and 15~18g of maleic anhydride is added, and are warming up to 80~120 DEG C, react 2~3h, Add 1~4g of tetrakis hydroxymetyl phosphonium sulfuric, be stirred to react 2~4h at 50~70 DEG C, add 0.02~0.03g of preservative and 0.01~0.04g of antioxidant, being neutralized with sodium carbonate to pH is 7~7.5, obtains the anti-flammability synthetic fat liquor.

The preservative is preservative or preservative PCP30.

The antioxidant is dibutyl hydroxy toluene or tert-butyl hydroquinone.

Advantage of the invention is that its main body is the physical treatment mode to blue leather bits, the basic of blue leather bits is not destroyed Form, for the chemical treatments that compare, processing cost is relatively low, does not generate secondary pollution.

Blue leather bits are that abrasion performance is poor, particle board is too hard for greatest problem present in particle board preparation, flexible Property difference and water imbibition it is strong, be easy to produce particle board contraction distortion, at the same poor fire, containing chromium ion migration the defects of, based on upper The defect stated, this invention takes corresponding technical measures.

It (1), is the ratio ratio of multiple spot combination in conjunction with single-point with the carboxyl of leather due to chromium ion most of in process hides tanning It is lower, and the stability that single-point combines is poor, therefore carries out appropriate detanning, the concentration of gained chrome liquor containing chromium to blue leather bits using oxalic acid It is used as tanning agent, by detanning, reduces the chromium ion to dissociate in shavings, and using trisodium citrate dihydrate to residual in shavings Remaining chromium ion is fixed, and the migration of subsequent chromium ion is reduced.

(2), it considers blue leather to be worth doing under larger pressure bonding using glue to get up, glue can harden after bonding, will cause in this way It is poor with flexibility that gained plate hardens, and the present invention improves its toughness using toughener, toughening synergist double action, uses simultaneously It with anti-flammability and reduces the synthetic fat liquor of leather hardness and reduces hardness, because hardness is too big, the particle board of bonding holds Easy to crack, synthetic fat liquor used uses sulfonic chloride, palm oil, neat's foot oil, with maleic anhydride, tetra methylol sulfuric acid Phosphorus reaction improves the caking property and toughness of particle board.

(3), it since the processing of particle board need to use high-temperature process, does not need fire retardant and leather carries out especially strong chemistry In conjunction with, therefore the present invention is using, with p-methyl benzene sulfonic chloride, dodecanedioic acid plays rush after dimethylphosphite, acrylamide reaction Into the reaction of p-methyl benzene sulfonic chloride, gained compound can be precipitated rapidly, convenient for collecting, since the fire retardant is increased to first Base benzene sulfonyl chloride increases phenyl ring and carbon source, also increases the anti-flammability and part toughness of leather indirectly.

(4), particle board needs to consider in use its abrasion resistance, and the present invention is on the basis of hardness, tan toughness On, the fixation that n-butylbenzoic acid, trimethylolpropane, cinnamamide increase particle plate surface is added, improves the resistance to of plate Wear hardness.

(5), particle board is in wet condition using meeting water swelling, and in order to solve this problem, the present invention uses hydroxyl Dimethyl silicone polymer, maleic anhydride, N- methyl alkyl amine and 2,5-furandicarboxylic acid reaction, gained plate have preferable anti- Water moisture pick-up properties, it is suppressed that the expansion of particle board.

Detailed description of the invention

Fig. 1 is the appearance figure of particle board prepared by the embodiment of the present invention one.

Specific embodiment

The present invention is further illustrated below with reference to embodiment and experiment effect data.

Particle board preparating example one

(1), blue leather bits 60g, oxalic acid 1g and 90g water are uniformly mixed, stir 1h at 35 DEG C；PH to 4 is adjusted again, is added Enter trisodium citrate dihydrate 0.4g, stir 30min, gained indigo plant skin chromium is considered to be worth doing and is dried；

(2), all blue leather bits of step (1), polyurethane adhesive 700w13.2g, nitrogen phosphorus flame retardant 2g, nitrile rubber are increased Tough dose of 1g, vinyl sodium benzosulfonate toughening synergist 0.2g, anti-flammability synthetic fat liquor 5g, inhibit water swelling agent 0.9g, just Butylbenzoic acid 0.7g, aqueous transparent waterproofing agent WP01 are uniformly mixed for 0.2g (Hangzhou Rui Jiang new material technology Co., Ltd), 30min is placed at normal temperature, is put on 4mm thickness mold, and vulcanizing press pressure is 10Mpa, and temperature is 90 DEG C, in compression molding Heating pressurization in machine, gained plate is placed into 48h in climatic chamber by process time 30min, controlled at 25 DEG C, Humidity is 65%, finally obtains the uniform plate of appearance and makees leather particles plate.

The preparation method of the inhibition water swelling agent: by hydroxyl dimethyl silicone polymer 15g, maleic anhydride 10g in 60 It is stirred to react 1h at~70 DEG C, N- methyl alkyl amine 1g and 2,5-furandicarboxylic acid 2.4g is added, stirs 20min at 50 DEG C, Obtain the inhibition water swelling agent.

The preparation method of the nitrogen phosphorus flame retardant: dimethylphosphite 50g is added in reaction vessel, is added Sodium methoxide 0.6g is simultaneously warming up to 75 DEG C, after sodium methoxide all dissolves, and addition 55g acrylamide cools to 40 DEG C, is added to methyl Benzene sulfonyl chloride 3.2g and dodecanedioic acid 0.4g, insulated and stirred reaction 1h obtain intermediate；It is added into intermediate last with 30% NaOH adjust pH 6.5, obtain nitrogen phosphorus flame retardant.

The preparation method of the anti-flammability synthetic fat liquor: by sulfonic chloride 15g, palm oil 10g, neat's foot oil 4g is warming up to 40 DEG C, and maleic anhydride 15g is added, and is warming up to 80 DEG C, reacts 2h, tetrakis hydroxymetyl phosphonium sulfuric 1g is added, in 50 DEG C Under be stirred to react 2h, add KS-20 (Jinan Kathon CG Chemical Co., Ltd.) 0.02g and dibutyl hydroxy toluene 0.01g, use carbon It is 7 that sour sodium, which is neutralized to pH, obtains the anti-flammability synthetic fat liquor.

Polyurethane adhesive 700w, nitrile rubber toughener and the vinyl sodium benzosulfonate toughening synergist is bought respectively It is limited in Nanguang Chemical Packing Co., Ltd., Nankai, Kang Gaote plastics Science and Technology Ltd., Jingjiang City, the Shanghai large biotechnology of connection Company.

Particle board preparating example two

(1), blue leather bits 60g, oxalic acid 3g and 90g water are uniformly mixed, stir 2h at 40 DEG C；PH to 4.5 is adjusted again, Trisodium citrate dihydrate 0.7g is added, stirs 60min, gained indigo plant skin chromium is considered to be worth doing and is dried；

(2), by all blue leathers bits of step (1), all-purpose adhesive 899 (Guangdong look after one's family Industrial Co., Ltd.) 21.1g, nitrogen phosphorus system Fire retardant 8g, polyvinyl butyral toughener 3g, malonic acid ring (Asia) isopropyl ester toughening synergist 0.5g, anti-flammability synthesis add Rouge agent 7g, inhibit water swelling agent 2.1g, trimethylolpropane 2.5g, aqueous transparent waterproofing agent WP01 for 0.6g (the auspicious Jiang Xin in Hangzhou Materials Technology Ltd.) it is uniformly mixed, 60min is placed at normal temperature, is put on 4mm thickness mold, and vulcanizing press pressure is 12Mpa, temperature are 100 DEG C, pressurization are heated in vulcanizing press, gained plate is placed into constant temperature by process time 60min 48h in constant humidity cabinet, controlled at 25 DEG C, humidity 65% finally obtains the uniform plate of appearance and makees leather particles plate.

Inhibit the preparation method of water swelling agent: hydroxyl dimethyl silicone polymer 15g, maleic anhydride 12g are stirred at 70 DEG C Reaction 2h is mixed, N- methyl alkyl amine 4g and 2,5-furandicarboxylic acid 3.6g is added, stirs 30min at 80 DEG C, obtain the inhibition water Swelling agent.

The preparation method of the nitrogen phosphorus flame retardant: dimethylphosphite 50g is added in reaction vessel, is added Sodium methoxide 2.2g is simultaneously warming up to 80 DEG C, after sodium methoxide all dissolves, and addition 85g acrylamide cools to 50 DEG C, is added to methyl Benzene sulfonyl chloride 6.8g and dodecanedioic acid 0.7g, insulated and stirred reaction 2h obtain intermediate；It is added into intermediate last with 30% NaOH adjust pH 6.5, obtain nitrogen phosphorus flame retardant.

The preparation method of the anti-flammability synthetic fat liquor is by sulfonic chloride 15g, palm oil 12g, cow hoof Oily 8g is warming up to 50 DEG C, and maleic anhydride 18g is added, and is warming up to 120 DEG C, reacts 3h, adds tetrakis hydroxymetyl phosphonium sulfuric 4g, in It is stirred to react 4h at 70 DEG C, adds PCP30 (spiral shell river chemical industry Shanghai Co., Ltd) 0.03g and tert-butyl hydroquinone 0.04g, Being neutralized with sodium carbonate to pH is 7.5, obtains the anti-flammability synthetic fat liquor.

The polyvinyl butyral toughener and malonic acid ring (Asia) isopropyl ester toughening synergist is bought respectively in Ji 100,000 Chemical Co., Ltd. of peaceful Bei Nuoke Biotechnology Co., Ltd, city and Shandong.

Particle board preparating example three

(1), blue leather bits 60g, oxalic acid 2g and 90g water are uniformly mixed, stir 1.5h at 40 DEG C；PH to 4 is adjusted again, Trisodium citrate dihydrate 0.55g is added, stirs 45min, gained indigo plant skin chromium is considered to be worth doing and is dried；

(2), all blue leather bits of step (1), polyurethane adhesive 700w17.2g, nitrogen phosphorus flame retardant 5g, polyvinyl alcohol are contracted Butyraldehyde toughener 2g, 3,4- dimethylaniline toughening synergist 0.35g, anti-flammability synthetic fat liquor 6g, inhibit water swelling agent 1.5g, cinnamamide 1.6g, aqueous transparent waterproofing agent WP01 are that 0.4g (Hangzhou Rui Jiang new material technology Co., Ltd) mixing is equal It is even, 45min is placed at normal temperature, is put on 4mm thickness mold, and vulcanizing press pressure is 11Mpa, and temperature is 95 DEG C, in plate Gained plate is placed into 48h in climatic chamber, controlled at 25 by heating pressurization, process time 45min in vulcanizer DEG C, humidity 65% finally obtains the uniform plate of appearance and makees leather particles plate.

Inhibit the preparation method of water swelling agent: hydroxyl dimethyl silicone polymer 15g, maleic anhydride 11g are stirred at 65 DEG C Reaction 1.5h is mixed, N- methyl alkyl amine 2.5g and 2,5-furandicarboxylic acid 3g is added, stirs 25min at 65 DEG C, obtain the inhibition Water swelling agent.

The preparation method of the nitrogen phosphorus flame retardant be dimethylphosphite 50g is added in reaction vessel, then plus Enter sodium methoxide 1.4g and be warming up to 75 DEG C, after sodium methoxide all dissolves, addition 70g acrylamide cools to 45 DEG C, is added to first Base benzene sulfonyl chloride 5g and dodecanedioic acid 0.55g, insulated and stirred reaction 1.5h obtain intermediate；Last use is added into intermediate 30% NaOH adjusts pH 6.5, obtains nitrogen phosphorus flame retardant；

The preparation method of the anti-flammability synthetic fat liquor is by sulfonic chloride 15g, palm oil 11g, cow hoof Oily 6g is warming up to 45 DEG C, and maleic anhydride 16.5g is added, and is warming up to 100 DEG C, reacts 2.5h, adds tetrakis hydroxymetyl phosphonium sulfuric 2.5g is stirred to react 3h at 60 DEG C, adds PCP30 (spiral shell river chemical industry Shanghai Co., Ltd) 0.02g and butylated hydroxy-a Benzene 0.01g, being neutralized with sodium carbonate to pH is 7.5, obtains the anti-flammability synthetic fat liquor.

The polyvinyl butyral toughener, 3,4- dimethylaniline toughening synergist are bought respectively in Jining City shellfish Nuo Ke Biotechnology Co., Ltd and island Hai Linuo Chemical Co., Ltd..

Below with reference to illustrating technical effect of the invention with test data:

(1), chromium ion is inhibited to migrate comparative experiments

The drying indigo plant leather bits that the step (1) of particle board preparating example one to three is obtained, are respectively placed in 100ml water and soak Bubble for 24 hours, is measured using elemental analyser, and chromium ion concentration (/ppm) is precipitated and is followed successively by 15,25 and 27.The quality such as same are blue Leather bits drying, is placed in 100ml water and is impregnated for 24 hours, measured using elemental analyser, precipitation chromium ion concentration 289ppm, 296ppm and 412ppm.It can be seen that effect of the technical measures of step (1) of the present invention in terms of inhibiting chromium ion migration is than more prominent.

(2), particle board anti-flammability is tested

Test method are as follows: ASTM E 662 and GB8323-87 defines smoke density measuring method, and oxygen index (OI) uses GB/ T5454-1997 is tested.

Vulcanizing press pressed sheet is cut into the template of 50mm × 50mm size, test examination using universal sampling machine The center dot thickness of sample, the diagonal line infall that central point is materialsed, is denoted as t1.Sample is immersed in pH=7 ± 1, temperature is It in the sink of (20 ± 1) DEG C, is maintained the temperature in prescribed limit during test, and makes specimen surface perpendicular to the water surface, and tried It is all larger than with sample and the distance between basin sidewall, bottom equal to 15mm between sample, distance is greater than etc. between sample and the water surface In (25 ± 5) mm.Sample is taken out after 20min, measures its center dot thickness.Particle board anti-flammability test data is shown in Table one.

Table 1

As can be found from Table 1, nitrogen phosphorus flame retardant and anti-flammability synthetic fat liquor play a part of anti-flammability, wherein hindering Combustion property synthetic fat liquor effect it is more special, general fatting agent be all play the role of it is combustion-supporting, if in anti-flammability Property, it being capable of the combustion-supporting effect of appropriate balance.

(3), particle board inhibits water expansion test

Toughness is judged by impact strength: plate is cut into the batten of 10mm × 80mm on universal sampling machine, is surveyed Width, the thickness for measuring its middle part edge and end center, are averaged the width and thickness for sample.When selecting pendulum, sample The energy for being broken consumption cannot be less than the 10% of pendulum gross energy, cannot be greater than the 90% of pendulum gross energy.It is hit having carried out sky After test, sample is placed on shock machine, starts to test, unit (impact strength/kjm^-2).Particle board inhibits water swollen Swollen test data is shown in Table 2.

Table 2

	Example one	Example two	Example three
				Thicken rate/%	3.5	4.2	2.6
Thicken rate/% (not plus N- methyl alkyl amine)	8.6	9.8	10.7
				Thicken rate/% (not plus 2,5- furandicarboxylic acid)	7.2	8.4	9.3
Thicken rate/% (unchecked water swelling agent)	11.3	12.4	10.4

As can be found from Table 2, if above-mentioned substance is not added for particle board, thickening property enhances, and the thickening property of comparative example 1 is 7.8%.

(4), particle board toughness test

It is tested according to GBT1843-2008 standard.Particle board toughness test data are shown in Table 3.

Table 3

Comparative example 1 is the experiment using orthogonal experiment 3, and basic parameter is table 6, and temperature 110, the time 70, resin added 16 is shown in Ding Shaolan etc., pressure sintering prepare the first exploratory developemnt of chrome shaving corium particle board, 2018,47 (12).

As can be found from Table 3, not plus toughener, toughening synergist impact strength (toughness) decline.

Separately as can be found from Table 3, toughness of the invention is better than comparative example 1.

(5), the wearability test of particle board

It is tested according to GB/T2726--2005 is examined, on the basis of 500 times.The wearability test of particle board the results are shown in Table 4。

Table 4

Comparative example 1 is the experiment using orthogonal experiment 3, and basic parameter is table 6, and temperature 110, the time 70, resin added 16 is shown in Ding Shaolan etc., pressure sintering prepare the first exploratory developemnt of chrome shaving corium particle board, 2018,47 (12).

By table 4 as it can be seen that particle board prepared by the present invention has preferable wear-resisting property.

The chromic oxide content of blue leather bits used in the embodiment of the present invention (is surveyed for 3.2% under the conditions of raw material skin over dry It is fixed), derive from Wendeng City Sen Lu tannery.