阅读说明：本技术 一种长效性农林保水剂及其制备方法 (Long-acting agriculture and forestry water-retaining agent and preparation method thereof ) 是由 柴松锋 于 2021-01-14 设计创作，主要内容包括：本发明涉及一种长效性农林保水剂及其制备方法,该农林保水剂由光稳定剂和紫外吸收剂分散到交联型丙烯酸/丙烯酸钾共聚物的聚合体系中,再经聚合和交联反应而得；除溶剂外的各组分在聚合体系中的质量百分数如下：丙烯酸单体70％～90％,氢氧化钾10％～30％,交联剂0.1‰～5‰,引发剂0.1‰～5‰,光稳定剂0.1‰～5‰,紫外吸收剂0.1‰～5‰；交联剂为复合交联剂,复合交联剂选自多元醇、多元胺、多元醇胺、多乙烯基化合物、多环氧化合物、多异氰酸酯化合物、多噁唑啉化合物、卤代环氧化合物、卤化物中的至少一种中至少两种不同的化合物。本发明的农林保水剂在起到保水作用的同时具有良好的强度和耐光照降解性。(The invention relates to a long-acting agriculture and forestry water-retaining agent and a preparation method thereof, wherein the agriculture and forestry water-retaining agent is prepared by dispersing a light stabilizer and an ultraviolet absorbent into a polymerization system of a cross-linking type acrylic acid/potassium acrylate copolymer, and then carrying out polymerization and cross-linking reaction; the mass percentages of the components except the solvent in the polymerization system are as follows: 70-90% of acrylic monomer, 10-30% of potassium hydroxide, 0.1-5% of cross-linking agent, 0.1-5% of initiator, 0.1-5% of light stabilizer and 0.1-5% of ultraviolet absorber; the cross-linking agent is a composite cross-linking agent, and the composite cross-linking agent is at least two different compounds selected from at least one of polyol, polyamine, polyalcohol amine, polyvinyl compound, polyepoxy compound, polyisocyanate compound, polyoxazoline compound, halogenated epoxy compound and halide. The agricultural and forestry water retention agent has a water retention effect and has good strength and light degradation resistance.)

1. The long-acting agriculture and forestry water-retaining agent is characterized in that the long-acting agriculture and forestry water-retaining agent is prepared by dispersing the light stabilizer and the ultraviolet absorbent into a polymerization system of the cross-linking type acrylic acid/potassium acrylate copolymer and then carrying out polymerization and cross-linking reaction; the polymerization system comprises the following components in percentage by mass except a solvent:

70 to 90 percent of acrylic monomer,

10 to 30 percent of potassium hydroxide,

0.1-5 per mill of cross-linking agent,

0.1 to 5 per mill of initiator,

0.1 to 5 per mill of light stabilizer,

ultraviolet absorbent 0.1-5 per mill;

the cross-linking agent is a composite cross-linking agent, and the composite cross-linking agent is at least two different compounds selected from at least one of polyol, polyamine, polyalcohol amine, polyvinyl compound, polyepoxy compound, polyisocyanate compound, polyoxazoline compound, halogenated epoxy compound and halide.

2. The long-acting agroforestry water-retaining agent according to claim 1, wherein:

the polyhydric alcohol is selected from polyester polyol, polyether polyol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 2-butene-1, 4-diol, carboxymethyl cellulose, diethanolamine, triethanolamine, diisopropanolamine; the polyether polyol is selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran glycol or copolymer thereof;

the polyamine is selected from ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, cyclohexyldiamine, hexamethylenediamine, isophoronediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, diaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, polyetheramine, chitosan or dopamine;

the polyalcohol amine is selected from ethanolamine, phenylethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2, 2-dimethylethanol, 2-amino-2-ethyl-1, 3-propanediol, tris (hydroxymethyl) aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane or 2-amino-2-methyl-1-butanol;

the polyvinyl compound is selected from polyethylene glycol di (meth) acrylate, N-methylenebisacrylamide, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, ethylene glycol di (meth) acrylate or 1, 4-butanediol di (meth) acrylate;

the polyepoxy compound is selected from polyester polyol diglycidyl ether, polyether polyol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, glycerol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, diglycerol polyglycidyl ether, bisphenol a epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin or aliphatic epoxy resin;

the polyisocyanate compound is selected from toluene diisocyanate, isophorone diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, naphthalene diisocyanate or isocyanate prepolymer;

the polyoxazoline compound is selected from 2,2' -bis (2-oxazoline) or 2,2- (1, 3-phenylene) -bisoxazoline;

the halogenated epoxy compound is selected from epichlorohydrin, epibromohydrin or alpha-methylepichlorohydrin;

the halide is selected from the group consisting of 1, 2-dibromoethane, 1, 2-dichloroethane, 1, 2-diiodoethane, 1, 3-dibromopropane, 1, 3-dichloropropane, 1, 3-diiodopropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-diiodobutane, 1, 5-dibromopentane, 1, 5-dichloropentane, 1, 5-diiodopentane, 1, 6-dibromohexane, 1, 6-dichlorohexane, 1, 6-diiodohexane, 2' -dichloroethyl ether, 1, 2-bis (2-chloroethoxy) ethane, diethylene glycol bis (2-chloroethyl) ether, triethylene glycol bis (2-chloroethyl) ether, 2' -dichloropropyl ether, 2' -dichlorobutyl ether or tetraethylene glycol bis (2-bromoethyl) ether.

3. The long-acting agroforestry water-retaining agent according to claim 2, wherein:

the composite cross-linking agent comprises low-molecular-weight polyol and high-molecular-weight polyol, wherein the mass ratio of the low-molecular-weight polyol to the high-molecular-weight polyol is 1: (0.3-3).

4. The long-acting water-retaining agent for agriculture and forestry as claimed in any one of claims 1 to 3, wherein:

the initiator is at least one of peroxide initiators, azo initiators and persulfate initiators;

the peroxide initiator is at least one selected from hydrogen peroxide, tert-butyl peroxide and methyl ethyl ketone peroxide;

the azo initiator is selected from at least one of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanonitrile, azodicyclohexyl cyanogen, azoisobutyryl formamide, azodiisobutyronitrile dimethyl ester, azodiisobutyl amidine hydrochloride and azodiisopropyl imidazoline hydrochloride;

the persulfate initiator is selected from at least one of sodium persulfate, potassium persulfate and ammonium persulfate.

5. The long-acting water-retaining agent for agriculture and forestry as claimed in any one of claims 1 to 3, wherein:

the light stabilizer is selected from at least one of hindered amine light stabilizer and benzoate light stabilizer;

the hindered amine light stabilizer is selected from ethyl bis (2, 2, 6, 6-tetramethylpiperazinone), 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, 2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-diazide-1, 3-malonic acid bis (1, 2,2, 6, 6-pentamethyl-4-piperidyl) ester, tetra (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butane tetracarboxylate, bis (2, 2, 6, 6-tetramethylpiperidyl) sebacate, resorcinol monobenzoate, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester, At least one of 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and tris (1, 2,2, 6, 6-pentamethylpiperidinyl) phosphite ester;

the benzoate light stabilizer is at least one of resorcinol monobenzoate, 3, 5-di-tert-butyl-4-hydroxybenzoic acid-2, 4-di-tert-butylphenyl ester and 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester.

6. The long-acting agroforestry water-retaining agent according to claim 5, wherein:

the light stabilizer is prepared from a hindered amine light stabilizer and a benzoate light stabilizer in a mass ratio of 1: (0.5-0.8).

7. The long-acting water-retaining agent for agriculture and forestry as claimed in any one of claims 1 to 3, wherein:

the ultraviolet absorbent is selected from 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, methylenebis (6-benzotriazol-4-tert-octylphenol), 2- [2, 4-bis (2, 4-xylyl) -2- (1,3, 5-triazinyl) 5-octyloxyphenol, 2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol), 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, phenyl o-hydroxybenzoate, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate, hexamethylphosphoric triamide, 2-benzoyl-4-methoxyphenol.

8. The long-acting water-retaining agent for agriculture and forestry as claimed in any one of claims 1 to 3, wherein:

the polymerization system also comprises 0.1 per thousand to 1 percent of coupling agent, 0.1 per thousand to 1 percent of defoaming agent and 0.1 per thousand to 1 percent of other functional additives by mass percent.

9. The preparation method of the long-acting agriculture and forestry water-retaining agent according to any one of claims 1 to 8, characterized by comprising the following steps:

the method comprises the following steps: dissolving potassium hydroxide in water to obtain an alkaline solution; mixing the alkaline solution with an acrylic acid monomer to obtain a first mixture, and carrying out acid-base neutralization reaction;

step two: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly mixing to obtain a second mixture;

step three: adding an initiator and a cross-linking agent into the second mixture to carry out polymerization and cross-linking reaction;

step four: and (4) filtering, crushing, drying and screening the product obtained in the step three to obtain the agricultural and forestry water-retaining agent.

10. The method of claim 9, wherein:

in the first step, the pH value of the first mixture is 6.0-8.0;

and in the fourth step, obtaining the granular agricultural and forestry water-retaining agent, wherein the mass ratio of the agricultural and forestry water-retaining agent with the granularity of 5-100 meshes is more than 80%.

Technical Field

The invention relates to the technical field of soil water retention, in particular to a long-acting agriculture and forestry water retention agent and a preparation method thereof.

Background

Water shortage is a serious problem facing countries in the world. At present, 80 countries in the world have insufficient water sources, 20 hundred million people cannot drink water, and 12 hundred million people face the threat of water shortage. The water shortage population is estimated to reach 28-33 hundred million people in 2025. This global shortage of water resources can have disastrous consequences.

China is a country with serious water shortage. According to measurement and calculation, the total amount of fresh water resources in the whole country is 28000 hundred million m³Account for the total of fresh water resources6% of the total amount, 2200m for each person³. Although the total amount is the fourth world, people all have 121 people in the world, which is 1/4 on the average level in the world, and the people are one of the 13 countries with the most poor water resources in the world. If water resources in flood runoff and rare-people-smoke areas which are difficult to utilize are deducted, the water resources which can be practically utilized nationwide are only 11000 hundred million m³900m for the left, the right and the average person³。

Besides the serious shortage of water resources in China, the water resource recycling method has the following characteristics:

1. the resource distribution is severely unbalanced: 81% of water resources in China are concentrated in the Yangtze river basin and the areas in the south of the Yangtze river basin, and the water resources of the three-north areas (northeast, northwest and northwest) which account for more than half of the cultivated land area in China are only 519m³1/20, which is the average level of the world.

2. The urban water shortage phenomenon is prominent: according to the statistics of the ministry of water conservancy, 400 cities in 669 cities in the country have insufficient water supply and 110 serious water shortage, and the total water shortage is 60 hundred million m³。

3. The phenomenon of 'over-mining' of water resources in the three north area is very serious: for example, 600 hundred million m of accumulated 'super-mining' underground water in Hebei province³In which 300 hundred million m³The deep groundwater cannot be supplemented. The serious 'super mining' makes the North China plain the largest underground composite funnel area in the world, with an area as large as 45 kilo square kilometers. For this reason, countries invest a large amount of capital annually for governance.

4. The water shortage and the cachexia caused by the water shortage are increasingly obvious: water shortage is the first major problem in China, and is one of the root causes of forest and grassland death in China. According to the statistical bulletin of water conservancy development in the nation in 2006 issued by the ministry of water conservancy, the drought-stricken area of crops in China in 2006 is 2073.8 ten thousand hectares. In the last 20 years, the yellow river is cut off almost annually, wherein the yellow river is cut off 226 days in 1997, and the Huaihe river is also cut off in nearly ten years. In addition, hundreds of lakes in the country are drying year by year, and many tributaries gradually disappear. According to the news network report in China, due to water shortage, the land desertification of 173.97 ten thousand square kilometers is shared by 889 counties (flags and districts) in 30 provinces in China, which accounts for 18 percent of the total area of the national soil, the production and the life of nearly 4 hundred million people are influenced, and the direct economic loss caused by each year is more than 500 hundred million yuan. As a serious water-deficit, the desertification area of land has reached 1203 ten thousand hectares, accounting for 28% of the total area of the whole province, with 94% of land being desertified in the civilian county that historically enjoyed the reputation of "oasis".

5. Agriculture is a big household that uses, lacks water and saves water: according to statistics, the annual agricultural water consumption accounts for 5500 hundred million m of the total national water consumption³More than 70%, wherein 9 is irrigation water. On one hand, the annual agricultural irrigation in China has 300 hundred million m of water shortage³(ii) a On the other hand, in national agriculture, most of the traditional modes of large water flood irrigation are adopted, the water utilization rate is as low as 40-45%, and the water is lost or volatilized by more than 2000 hundred million m³And (3) water.

The facts show that water resources are increasingly deficient, and the living environment of human beings is seriously threatened. A plurality of methods are invented to obtain certain effects after a plurality of efforts are invested by governments and people in full of brain juice. There are many main methods used today, such as: drip irrigation, mulching, cultivation of improved crop seeds, and application of agricultural and forestry water retention agents. The drip irrigation method and the mulching film method have direct effect and too high input cost, and can cause secondary white pollution; the difficulty of good breed cultivation is too large, and drought-resistant varieties of various plants are difficult to screen; the agriculture and forestry water retention agent method is an optimal scheme at present.

The agricultural and forestry water-retaining agent is also called water-retaining agent, soil water-retaining agent, drought-resisting water-retaining agent, soil moisture-preserving agent, antitranspirant, fertilizer-storing agent or micro reservoir, etc., is a functional high-molecular polymer with three-dimensional network structure, and has obvious water-absorbing, water-storing and water-retaining properties. Because the molecules are in a unique three-dimensional network structure and contain strong hydrophilic groups, the water-absorbing agent has strong association effect on water through osmotic pressure generated by electrolyte ion concentration inside and outside the molecules, and can usually absorb 300-500 times of pure water rapidly, so that rainwater or irrigation water evaporated, permeated and lost in the past can be absorbed and stored to form 'solid water'. A 'small reservoir' is formed in the soil at the root of the plant, which is beneficial to the continuous absorption and growth of the plant, 'wet absorption and dry release' and the circulation is repeated, so that a benign mechanism for supplying water to the plant for a long time is formed, and the water saving rate is as high as more than 50%. In addition, the water-retaining agent has the effects of absorbing and storing fertilizers and pesticides, can prolong the fertilizer period of the fertilizers and the pesticides, loosen and ventilate soil, improve beneficial microbial groups in the soil and the like, can obviously improve the survival rate and the yield of crops, is increasingly paid attention to all countries in the world in recent years, and has made good progress in the aspect of market development.

At present, the mainstream method of the agricultural and forestry water-retaining agent is an aqueous solution polymerization method, acrylic acid is neutralized, an initiator is added to initiate an aqueous solution system containing potassium acrylate-acrylic acid to carry out polymerization reaction, and then the procedures of crushing, granulating, drying, crushing, post-processing, screening and the like are carried out, so as to prepare the agricultural and forestry water-retaining agent. Its advantages are low cost, no need of recovering organic solvent, safe preparing process and no generation of three wastes. The defect is that the product has poor light degradation resistance, so that the effective service life of the product is greatly shortened, and the service life of 3-5 years which is nominal by each manufacturer is difficult to achieve.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an agricultural and forestry water retention agent which is resistant to light degradation and has a good water retention effect and a preparation method thereof.

In order to realize the aim of the invention, the invention provides a long-acting agriculture and forestry water-retaining agent, which is prepared by dispersing the light stabilizer and the ultraviolet absorbent into a polymerization system of the cross-linking type acrylic acid/potassium acrylate copolymer and then carrying out polymerization and cross-linking reaction; the polymerization system comprises the following components in percentage by mass except a solvent: 70-90% of acrylic monomer, 10-30% of potassium hydroxide, 0.1-5% of cross-linking agent, 0.1-5% of initiator, 0.1-5% of light stabilizer and 0.1-5% of ultraviolet absorber; the cross-linking agent is a composite cross-linking agent, and the composite cross-linking agent is at least two different compounds selected from at least one of polyol, polyamine, polyalcohol amine, polyvinyl compound, polyepoxy compound, polyisocyanate compound, polyoxazoline compound, halogenated epoxy compound and halide.

Preferably, the polyol is selected from polyester polyols, polyether polyols, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 2-butene-1, 4-diol, carboxymethyl cellulose, diethanolamine, triethanolamine, diisopropanolamine; the polyether polyol is selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran glycol or their copolymer. The polyethylene glycol can be polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 1500, polyethylene glycol 4000, polyethylene glycol 6000, polyethylene glycol 8000, polyethylene glycol 10000, polyethylene glycol 20000, etc.

Preferably, the polyamine is selected from ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, nonylenediamine, cyclohexylenediamine, hexamethylenediamine, isophoronediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, diaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, polyetheramine, chitosan, or dopamine.

Preferably, the polyalcohol amine is selected from ethanolamine, phenylethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2, 2-dimethylethanol, 2-amino-2-ethyl-1, 3-propanediol, tris (hydroxymethyl) aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane or 2-amino-2-methyl-1-butanol.

Preferably, the polyvinyl compound is selected from polyethylene glycol di (meth) acrylate, N-methylenebisacrylamide, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, ethylene glycol di (meth) acrylate or 1, 4-butanediol di (meth) acrylate.

Preferably, the polyepoxy compound is selected from polyester polyol diglycidyl ether, polyether polyol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, glycerol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, diglycerol polyglycidyl ether, bisphenol a type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin.

Preferably, the polyisocyanate compound is selected from toluene diisocyanate, isophorone diisocyanate, 1, 6-hexyl diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, naphthalene diisocyanate or an isocyanate prepolymer.

Preferably, the polyoxazoline compound is selected from 2,2' -bis (2-oxazoline) or 2,2- (1, 3-phenylene) -bisoxazoline.

Preferably, the halogenated epoxy compound is selected from epichlorohydrin, epibromohydrin or alpha-methylepichlorohydrin.

Preferably, the halide is selected from the group consisting of 1, 2-dibromoethane, 1, 2-dichloroethane, 1, 2-diiodoethane, 1, 3-dibromopropane, 1, 3-dichloropropane, 1, 3-diiodopropane, 1, 4-dibromobutane, 1, 4-dichlorobutane, 1, 4-diiodobutane, 1, 5-dibromopentane, 1, 5-dichloropentane, 1, 5-diiodopentane, 1, 6-dibromohexane, 1, 6-dichlorohexane, 1, 6-diiodohexane, 2 '-dichloroethyl ether, 1, 2-bis (2-chloroethoxy) ethane, diethylene glycol bis (2-chloroethyl) ether, triethylene glycol bis (2-chloroethyl) ether, 2' -dichloropropyl ether, 2,2' -dichlorobutyl ether or tetraethyleneglycol bis (2-bromoethyl) ether.

Preferably, the composite crosslinking agent comprises a low-molecular (molecular weight less than 1000) crosslinking agent and a high-molecular (molecular weight greater than 1000) crosslinking agent, and the mass ratio of the low-molecular crosslinking agent to the high-molecular crosslinking agent is 1: (0.3-3).

Preferably, the initiator is selected from at least one of peroxide initiators, azo initiators, and persulfate initiators.

Preferably, the peroxide initiator is at least one selected from hydrogen peroxide, tert-butyl peroxide and methyl ethyl ketone peroxide.

Preferably, the azo initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobiscyclohexylcyanogen, azobisisobutyronitrile formamide, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride and azobisisopropylimidazoline hydrochloride.

Preferably, the persulfate initiator is at least one selected from the group consisting of sodium persulfate, potassium persulfate, and ammonium persulfate.

Preferably, the light stabilizer is selected from at least one of hindered amine light stabilizers and benzoate light stabilizers.

Preferably, the hindered amine light stabilizer is selected from the group consisting of ethylbis (2, 2, 6, 6-tetramethylpiperazinone), 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, bis (1, 2,2, 6, 6-pentamethyl-4-piperidinyl) 2- (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-diazide-1, 3-malonate, tetrakis (2, 2, 6, 6-tetramethyl-4-piperidinyl) -1, 2, 3, 4-butanetetracarboxylate, bis (2, 2, 6, 6-tetramethylpiperidinyl) sebacate, resorcinol monobenzoate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, resorcinol, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester and tris (1, 2,2, 6, 6-pentamethylpiperidinyl) phosphite.

Preferably, the benzoate light stabilizer is at least one of resorcinol monobenzoate, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

Preferably, the light stabilizer consists of a hindered amine light stabilizer and a benzoate light stabilizer in a mass ratio of 1: (0.5-0.8).

Preferably, the UV absorber is selected from the group consisting of 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butylphenyl) -benzotriazole, methylenebis (6-benzotriazol-4-tert-octylphenol), 2- [2, 4-bis (2, 4-xylyl) -2- (1,3, 5-triazinyl) 5-octyloxyphenol, 2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol), 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, phenyl o-hydroxybenzoate, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate, hexamethylphosphoric triamide, 2-benzoyl-4-methoxyphenol.

Preferably, the polymerization system also comprises 0.1 per thousand to 1 percent of coupling agent, 0.1 per thousand to 1 percent of defoaming agent and 0.1 per thousand to 1 percent of other functional auxiliary agent according to the mass percentage.

In order to realize another purpose of the invention, the invention provides a preparation method of the long-acting agriculture and forestry water-retaining agent, which comprises the following steps:

the method comprises the following steps: dissolving potassium hydroxide in water to obtain an alkaline solution; mixing the alkaline solution with an acrylic acid monomer to obtain a first mixture, and carrying out acid-base neutralization reaction;

step two: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly mixing to obtain a second mixture;

step three: adding an initiator and a cross-linking agent into the second mixture to carry out polymerization and cross-linking reaction;

step four: and (4) filtering, crushing, drying and screening the product obtained in the step three to obtain the agricultural and forestry water-retaining agent.

Preferably, in the first step, the pH value of the first mixture is 6.0-8.0.

Preferably, in the fourth step, the granular agricultural and forestry water-retaining agent is obtained, and the mass ratio of the agricultural and forestry water-retaining agent with the granularity of 5-100 meshes is more than 80%.

Compared with the prior art, the invention can obtain the following beneficial effects:

the agricultural and forestry water retention agent has good gel strength and light degradation resistance while playing a role in water absorption and water retention. The cross-linked acrylic acid/potassium acrylate copolymer is used as a functional polymer water absorption material, the molecules of the cross-linked acrylic acid/potassium acrylate copolymer contain a large number of hydrophilic groups, water which is hundreds of times of the weight of the copolymer can be absorbed and maintained in a short time, and the copolymer can be slowly released and repeatedly absorbed, so that a good water retention and water saving effect is achieved; the water-absorbing gel has high strength, repeatedly absorbs expansion and release, can loosen soil, keep the permeability of the soil, prevent the soil from hardening and create a good soil environment for plant growth. The light stabilizer and the ultraviolet absorber are selectively added and uniformly dispersed and combined into the cross-linked acrylic acid/potassium acrylate copolymer long-chain molecule, so that the degradation of a high polymer caused by the breakage of a molecular chain of the long-chain molecule under the action of external energy such as sunlight, ultraviolet rays and the like is effectively avoided, the light degradation resistance of the agriculture and forestry water-retaining agent is obviously improved, and the service life of the agriculture and forestry water-retaining agent is greatly prolonged. The accelerated aging test in a laboratory shows that under the same condition, the light degradation resistance of the agriculture and forestry water-retaining agent improved by the invention is improved by more than 3-5 times compared with the original agriculture and forestry water-retaining agent (comprising various water-retaining agents in the current market), so that the use validity period of the agriculture and forestry water-retaining agent is greatly improved, the use times and the cost are reduced, and the economic benefit and the social benefit are very obvious. The agricultural and forestry water retention agent can be gradually decomposed into carbon dioxide, water, nitrogen and other small molecular substances after being used in soil for 5-10 years, is beneficial and harmless to the soil, and is a real green high-tech product.

In addition, the invention adopts the composite cross-linking agent, can effectively control the implosion caused by the over-fast polymerization reaction process, and avoids the formation of a large amount of pore structures in the polymer due to the implosion, so that the final product has low gel strength after absorbing water, is used repeatedly for a few times and is difficult to achieve the purpose of long-term use.

Detailed Description

Example 1

The agricultural and forestry water-retaining agent of the embodiment is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer, which consists of 14g of ethylbis (2, 2, 6, 6-tetramethylpiperazinone) and 11g of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Example 2

The agricultural and forestry water-retaining agent of the embodiment is prepared by the following steps:

preparing raw materials: 3500g of acrylic monomer; 1500g of potassium hydroxide; 25g of cross-linking agent, which consists of 10g of diethylene glycol and 200015 g of polyethylene glycol; 5g of azodiisobutyronitrile serving as an initiator; 7800g of deionized water; 15g of a light stabilizer consisting of tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butanetetracarboxylate 10g and resorcinol monobenzoate 5 g; 5g of ultraviolet absorbent hexamethyl phosphoric triamide;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing an alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 50 ℃ to perform acid-base neutralization reaction for 2 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 80 ℃ for 6 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Example 3

The agricultural and forestry water-retaining agent of the embodiment is prepared by the following steps:

preparing raw materials: 4500g of acrylic monomer; 500g of potassium hydroxide; 5g of cross-linking agent, which consists of 1.5g of ethylene glycol diglycidyl ether and 3.5g of polyethylene glycol diglycidyl ether; 25g of initiator ammonium persulfate; 4500g of deionized water; 5g of light stabilizer, which consists of 3g of 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine and 2g of 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 25g of ultraviolet absorbent 2, 4-dihydroxy benzophenone;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with acrylic monomer to obtain a first mixture, stirring at 60 ℃ to perform acid-base neutralization reaction for 2 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 7 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 1

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; the cross-linking agent is composed of 20g of N, N-methylene-bisacrylamide; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer, which consists of 14g of ethylbis (2, 2, 6, 6-tetramethylpiperazinone) and 11g of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 2

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; 20g of cross-linking agent polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer, which consists of 14g of ethylbis (2, 2, 6, 6-tetramethylpiperazinone) and 11g of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 3

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer ethylbis (2, 2, 6, 6-tetramethylpiperazinone); 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 4

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 5

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4000g of acrylic acid monomer; 1000g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding an initiator and a cross-linking agent into the first mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and step 3: and (3) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (2) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 6

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 4800g of acrylic monomer; 200g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer, which consists of 14g of ethylbis (2, 2, 6, 6-tetramethylpiperazinone) and 11g of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

Comparative example 7

The agricultural and forestry water-retaining agent of the comparative example is prepared by the following steps:

preparing raw materials: 3200g of acrylic monomer; 1800g of potassium hydroxide; 20g of cross-linking agent, which is composed of 15g of N, N-methylene bisacrylamide and 5g of polyethylene glycol dimethacrylate; 11g of initiator benzoyl peroxide; 5100g of deionized water; 25g of light stabilizer, which consists of 14g of ethylbis (2, 2, 6, 6-tetramethylpiperazinone) and 11g of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; 10g of ultraviolet absorbent 2- (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole;

step 1: dissolving potassium hydroxide in deionized water to obtain an alkaline solution; mixing the alkaline solution with an acrylic monomer to obtain a first mixture, stirring at 25 ℃ to perform acid-base neutralization reaction for 3 hours;

step 2: adding a light stabilizer and an ultraviolet absorber into the first mixture, and uniformly stirring to obtain a second mixture;

and step 3: adding an initiator and a cross-linking agent into the second mixture, uniformly stirring, and then carrying out polymerization and cross-linking reaction at 60 ℃ for 8 hours;

and 4, step 4: and (4) filtering, crushing, granulating, drying, grinding and screening the product obtained in the step (3) to obtain the agriculture and forestry water-retaining agent, and then packaging and warehousing the product.

The test results of the agroforestry water-retaining agent obtained in examples 1 to 3 and comparative examples 1 to 7 are shown in table 1 below. The test result of the photodegradation time of the agriculture and forestry water-retaining agent is tested by adopting the following method: various water-retaining agents absorb water in a saturated mode, the formed gel is directly exposed to the sun, the change condition of the gel is observed, the water-retaining agents soften firstly, then the water is dissolved, the water absorbing and retaining functions are completely lost, and the time of completely dissolving the water is the degradation time.

TABLE 1 test results of agroforestry water-retaining agent

Example numbering	Amount of distilled water absorbed (g/g)	Gel strength after water absorption	Degradation time (h)
				Example 1	450	Good effect	45
Example 2	480	Good effect	50
				Example 3	430	Good effect	62
Comparative example 1	410	Difference (D)	35
				Comparative example 2	420	Medium and high grade	37
Comparative example 3	440	Good effect	32
				Comparative example 4	440	Good effect	28
Comparative example 5	445	Good effect	13
				Comparative example 6	280	Good effect	25
Comparative example 7	300	Difference (D)	22

Therefore, the polymerization system adopting a single cross-linking agent, for example, the small-molecular cross-linking agent is easy to implode, the polymerization reaction process is too fast, and a large amount of pore structures are easy to form in the polymer, so that the final product has low gel strength after absorbing water, is less in repeated use and difficult to achieve the purpose of long-term use, and the appearance of the water-retaining agent is difficult to control due to the too fast polymerization, and has adverse effect on water absorption performance; the adoption of a single macromolecular cross-linking agent easily causes the over-slow cross-linking speed and the over-low cross-linking degree, and is not favorable for the water absorption performance and the gel strength after water absorption. The water absorbent without adding the light stabilizer or the ultraviolet light absorber has obvious degradation in the sun, and the light degradation resistance is improved after the light stabilizer or the ultraviolet light absorber is added. Under the coordination of the compound light stabilizer and the ultraviolet light absorber, the light degradation resistance can be further improved under the same addition amount, and the best light degradation resistance level in the current market is achieved. In addition, the pH value of the polymerization system is moderate, the influence of the water-retaining agent on the acidity and alkalinity of soil is reduced, the influence of the acidity and alkalinity on the polymerization reaction is also reduced, the polymerization reaction of the crosslinking type acrylic acid/potassium acrylate copolymer can be smoothly carried out, the ratio of acrylic acid/potassium acrylate is moderate, and the water retention performance is improved.

The agricultural and forestry water-retaining agent can be applied to afforestation, sapling cultivation, lawn planting, desert control, seed coating, seed granulation and the like. The application method can adopt a wet application method: putting the agriculture and forestry water-retaining agent into a container with the mass ratio of 1: 150 hours, fully absorbing water for 0.5-6 hours, and adding required fertilizer; and (3) applying the agriculture and forestry water-retaining agent gel particles after fully absorbing water into the dug holes and ditches, uniformly mixing the gel particles with soil which is 3-5 times of the weight of the gel particles, then planting plants in the holes (ditches), covering a layer of soil, and irrigating a proper amount of water. Dry application methods may also be employed: directly putting a proper amount of the agriculture and forestry water-retaining agent into the dug holes and ditches, wherein the mass ratio of the agriculture and forestry water-retaining agent to the agriculture and forestry water-retaining agent is 1: and (2) uniformly mixing 500-1000 soil, planting plants in the holes and the ditches, then irrigating a large amount of water to fully absorb the agriculture and forestry water-retaining agent to a saturated state, and finally covering a layer of soil.

Finally, it should be emphasized that the above-described embodiments are merely preferred examples of the invention, which is not intended to limit the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.